Transition metal complexes, catalyst compositions containing the same, and olefin polymerization using the catalyst compositions

ABSTRACT

Provided are a novel transition metal complex where a monocyclopentadienyl ligand to which an amido or alcoxy group is introduced is coordinated, a method of synthesizing the same, and olefin polymerization using the transition metal complex. Compared to a conventional transition metal complex having a silicon bridge and an oxido ligand, the transition metal complex has a phenylene bridge, so that a monomer easily approaches the transition metal complex in terms of structure and a pentagon ring structure of the transition metal complex is stably maintained. The catalyst composition including the transition metal complex is used to synthesize a polyolefin copolymer having a very low density less than 0.910 g/cc.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application claims the benefit of Korean Patent Application No.10-2005-0061820, filed on Jul. 8, 2005, in the Korean IntellectualProperty Office, the disclosure of which is incorporated herein in itsentirety by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel transition metal complex wherea monocyclopentadienyl ligand to which an amido or alcoxy group isintroduced is coordinated, a method of synthesizing the same, and olefinpolymerization using the transition metal complex, and moreparticularly, to a novel transition metal complex containing a phenylenebridge, a method of synthesizing the same, and olefin polymerizationusing the transition metal complex.

2. Description of the Related Art

In the early 1990s, Dow Co. developed Me₂Si(Me₄C5)(NtBu)TiCl₂(Constrained-Geometry Catalyst, hereinafter referred to as CGC) (U.S.Pat. No. 5,064,802). CGC shows excellent properties in acopolymerization reaction of ethylene and alpha-olefin, compared toconventional metallocene catalysts. For example, (1) CGC can be used toform high molecular weight polymers due to its high reactivity at highpolymerization temperature, and (2) CGC can be used for copolymerizationof alpha-olefin having large steric hindrance, such as 1-hexene and1-octene. Due to many useful properties, in addition to these propertiesdescribed above, obtained from use of CGC, research into synthesis ofCGC derivatives as a polymerization catalyst is substantially increasingin academic and industrial fields.

For example, synthesis of metal complexes comprising other variousbridges instead of a silicon bridged CGC and containing a nitrogensubstituent, and polymerization using these metal complexes wereperformed. Examples of such metal compounds include Complexes 1 through4 (Chem. Rev. 2003, 103, 283).

Complexes 1 through 4 respectively contain a phosphorus bridge, anethylene or propylene bridge, a methylidene bridge, and a methylenebridge, instead of the silicon bridge of the CGC structure. However,these complexes show low activity or poor copolymerization performancewhen ethylene is polymerized or when ethylene and alpha-olefin arecopolymerized, compared to CGC.

In addition, the amino ligand in CGC can be replaced with an oxidoligand. some of such complexes were used for polymerization. Examples ofsuch complexes include:

In Complex 5, which was developed by T. J. Marks et al., acyclopentadiene (Cp) derivative is bridged to an oxido ligand byortho-penylene group (Organometallics 1997, 16, 5958). A complex havingthe same bridge and polymerization using the compound were suggested byMu et al. (Organometallics 2004, 23, 540). A complex in which an indenylligand is bridged to an oxido ligand by an ortho-phenylene group wasdeveloped by Rothwell et al. (Chem. Commun. 2003, 1034). In Complex 6,which was developed by Whitby et al., a cyclopentadienyl ligand isbridged to an oxido ligand by three carbon atoms (Organometallics 1999,18, 348). It was reported that Complex 6 showed reactivity insyndiotactic polystyrene polymerization. Similar complexes to Complex 6were developed by Hessen et al. (Organometallics 1998, 17, 1652).Complex 7, which was developed by Rau et al., showed reactivity whenbeing used for ethylene polymerization and ethylene/1-hexencopolymerization at high temperature and high pressure (210° C., 150Mpa) (J. Organomet. Chem. 2000, 608, 71). Complex 8, which has a similarstructure to Complex 7, can be used for high temperature, high pressurepolymerization, which was applied to US Patent Office by Sumitomo Co.(U.S. Pat. No. 6,548,686).

However, only some of these catalysts described above are used incommercial industry. Accordingly, there is still a need to develop acatalyst inducing high polymerization performance.

SUMMARY OF THE INVENTION

The present invention provides a novel transition metal complex having aphenylene bridge.

The present invention also provides a novel organic amine-basedcompound.

The present invention also provides a novel organic ketone-based boronicacid compound.

The present invention also provides a method of preparing the transitionmetal complex.

The present invention also provides a catalyst composition containingthe transition metal complex.

The present invention also provides a method of preparing the catalystcomposition.

The present invention also provides a method of preparing a polymerusing the catalyst composition.

The present invention also provides a polymer prepared using the methodof preparing a polymer using the catalyst composition.

According to an aspect of the present invention, there is provided atransition metal complex of Formula 1:

where R₁ and R₂ are each independently a hydrogen atom; a C1-C20 alkyl,aryl, or silyl radical; a C1-C20 alkenyl, alkylaryl, or arylalkylradical; or a metalloid radical of Group 14 metal substituted withhydrocarbyl, wherein R₁ and R₂ can be connected by an alkylidine radicalthat contains a C1-C20 alkyl or aryl radical to form a ring;

R₄ is each independently a hydrogen atom; a halogen radical; or a C1-C20alkyl or aryl radical, wherein two R₄ are connected to form a fused ringstructure;

R₃ is a C1-C20 alkyl sulfonyl, aryl sulfonyl, or silyl sulfonyl radical;a C1-C20 alkyl carbonyl, aryl carbonyl, or silyl carbonyl radical;C1-C20 alkyl carboxy, or aryl carboxy radical; or C1-C20 alkylphosphonyl, or aryl phosphonyl radical;

M is a transition metal of Group 4; and

Q₁ and Q₂ are each independently a halogen radical; a C1-C20 alkyl oraryl amido radical; a C1-C20 alkyl, alkenyl, aryl, alkylaryl, orarylalkyl radical; or a C1-C20 alkylidene radical.

The transition metal complex of Formula 1 may be represented by Formula14:

where R₁₁ and R₁₂ are each independently hydrogen atom; or C1-C20 alkyl,aryl, or silyl radical;

R₁₄ is each independently hydrogen atom; a C1-C20 alkyl radical; orhalogen radical;

Q₃ and Q₄ are each independently a halogen radical; C1-C20 alkyl, oraryl amido radical; or C1-C20 alkyl radical;

M is a transition metal of Group 4; and

R₈ is

where Y is a carbon atom or a sulfur atom;

R₉ is a hydrogen atom; a C1-C20 alkyl, aryl, or silyl radical; or aC1-C20 alkoxy, or aryloxy radical; and

when Y is the carbon atom, n is 1, and when Y is the sulfur atom, n is2.

The transition metal complex of formula 1 may be represented by one offormulae below:

where R₁₀ is methyl, tosyl, mesityl, or t-butyl radical; Q₅ and Q₆ areeach independently methyl a dimethylamido radical or a chloride radical.

According to another aspect of the present invention, there is provideda transition metal complex of Formula 2:

where R₁, R₂, R₄, M, Q₁ and Q₂ are described above;

G is an oxygen atom or a sulfur atom; and

R₅ is a hydrogen atom; a C1-C20 alkyl or aryl radical; or a C1-C20alcoxy or aryloxy radical.

According to another aspect of the present invention, there is provideda transition metal complex of Formula 3:

where R₁, R₂, R₄, R₅, M, Q₁, and Q₂ are described above; and G′ is anoxygen atom, a sulfur atom, or a substituted nitrogen group (—NR) whereR is a C1-C20 alkyl or aryl radical.

The transition metal complexes of formula 2 or formula 3 may berepresented by:

where R₁₁, R₁₂, R₁₄, Q₃, Q₄, M, and R₅ are described above, and G″ is anoxygen atom, a sulfur atom, or a substituted nitrogen group where asubstituent is a C1-C20 alkyl or aryl amido radical.

The transition metal complexes of formula 2 or formula 3 may berepresented by one of formulae below:

where R₁₅ is methyl radical, t-butyl radical, or t-butoxy radical; Q₅and Q₆ are described above; and X is a halogen radical.

According to another aspect of the present invention, there is providedamine-based compounds of Formulae 4 through Formula 7:

where R₁, R₂, R₃, and R₄ are described above.

According to another aspect of the present invention, there is providedan organic ketone-based boronic acid compound of Formula 8:

where R₁ and R₂ are described above.

According to another aspect of the present invention, there is provideda method of synthesizing a transition metal complex, the methodincluding:

synthesizing a compound of Formula 6 by reacting a boronic acid compoundof Formula 8 with a 2-bromoaniline compound of Formula 9;

synthesizing a compound of Formula 5 by the compound of Formula 6 withR₃X where X is a halogen atom;

synthesizing a compound of Formula 4 by reacting a compound of Formula 5with R₁Li and then adding an acid thereto; and

synthesizing a complex of Formula 1 or Formula 2 by reacting thecompound of Formula 4 with the compound of Formula 10 and then adding(CH₃)_(n)SiX_(4-n) where X is a halogen atom and n is 0, 1, 2, or 3thereto:

where R₄ is each independently a hydrogen atom; a halogen radical; or aC1-C20 alkyl or aryl radical, wherein two R₄ are connected to form afused ring structure; andM(N(R₆)₂)₄  (10)where M is a transition metal of Group 4, and

R₆ is a C1-C20 alkyl or aryl radical.

According to another aspect of the present invention, there is provideda method of synthesizing a transition metal complex, the methodincluding:

synthesizing a compound of Formula 6 by reacting a boronic acid compoundof Formula 8 with a 2-bromoaniline compound of Formula 9;

synthesizing a compound of Formula 7 by the compound of Formula 6 withR₁Li and then adding an acid thereto;

synthesizing a compound of Formula 4 by reacting a compound of Formula 7with R₃X where X is a halogen atom; and

synthesizing a complex of Formula 1 or Formula 2 by reacting thecompound of Formula 4 with the compound of Formula 10 and then adding(CH₃)_(n)SiX_(4-n) where X is a halogen atom and n is 0, 1, 2, or 3thereto.

According to another aspect of the present invention, there is provideda method of synthesizing a transition metal complex, the methodcomprising:

synthesizing a dilithium form of the compound of Formula 7 by reacting acompound of Formula 7 with an alkyllithium that is a base; and

synthesizing a complex of Formula 3 by reacting an in-situe mixturecomposed of the dilithium compound, alkyllithium, and MX₄ where X ishalogen and M is a transition metal of Group 4.

According to another aspect of the present invention, there is providedcatalyst composition including:

the transition metal complex of any one of formulaes 1, 2, and 3; and

at least one cocatalyst compound selected from compounds of Formulae 11through 13:—[Al(R₇)—O]_(a)—  (11)where R₇ is each independently a halogen radical; a C1-C20 hydrocarbylradical; or a C1-C20 hydrocarbyl radical substituted with halogen; and

a is an integer of 2 or greater;D(R₇)₃  (12)where D is aluminum or boron; and R₇ is described above; and[L—H]⁺[Z(A)₄]⁻, or [L]⁺[Z(A)₄]⁻  (13)where L is a neutral or cationic Lewis acid;

H is a hydrogen atom;

Z is an element of Group 13;

A is each independently a C6-C20 aryl or alkyl radical in which at leastone hydrogen atom is substituted with halogen or a C1-C20 hydrocarbyl,alcoxy, or phenoxy radical.

According to another aspect of the present invention, there is provideda method of preparing a catalyst composition, the method including:

contacting the transition metal complex of any one of formulaes 1, 2,and 3 with the compound of Formula 11 or Formula 12, thereby obtaining amixture; and

adding a compound of Formula 13 to the mixture.

The mole ratio of the transition metal complex to the compound ofFormula 11 or Formula 12 may be in the range of 1:2 through 1:5000, andthe mole ratio of the transition metal complex of the compound ofFormula 13 may be in the range of 1:1 through 1:25.

According to another aspect of the present invention, there is provideda method of synthesizing an olefin polymer, including contacting thecatalyst composition with a monomer.

The monomer may contain at least one monomer selected from the groupconsisting of ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-hepthene, 1-octene, 1-decene,1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-itosen.

According to another aspect of the present invention, there is providedan olefin polymer synthesized using the method of synthesizing an olefinpolymer.

The monomer that is used to synthesize the olefin polymer may include:ethylene; and at least one compound selected from the group consistingof propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other features and advantages of the present inventionwill become more apparent by describing in detail exemplary embodimentsthereof with reference to the attached drawings in which:

FIG. 1 illustrates an X-ray structure of(p-toluenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumbis(dimethylamide) that is a transition metal complex according to anembodiment of the present invention;

FIG. 2 illustrates an X-ray structure of4,6-difluorophenylene(t-butyliminooxy)(2,5-dimethylcyclopentadienyl)-titaniumdichloride that is a transition metal complex according to anotherembodiment of the present invention; and

FIG. 3 illustrates an X-ray structure ofphenylene(t-butylcarboxamido)(2,5-dimethylcyclopentadienyl)titaniumdimethyl that is a transition metal complex according to anotherembodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described more fully with reference tothe accompanying drawings.

A transition metal complex according to an embodiment of the presentinvention has a phenylene bridge, so that a sterically hindered monomereasily approaches the transition metal complex and a pentagon ringstructure of the transition metal complex is stably maintained, comparedto a conventional transition metal complex having a silicon bridge andan oxido ligand. By using a catalyst composition including thetransition metal complex according to an embodiment of the presentinvention, a polyolefin copolymer having a very low density less than0.910 g/cc can be obtained.

A transition metal complex according to an embodiment of the presentinvention may be represented by Formula 1:

where R₁ and R₂ are each independently a hydrogen atom; a C1-C20 alkyl,aryl, or silyl radical; a C1-C20 alkenyl, alkylaryl, or arylalkylradical; or a metalloid radical of Group 14 metal substituted withhydrocarbyl, wherein R₁ and R₂ can be connected by an alkylidine radicalthat contains a C1-C20 alkyl or aryl radical to form a ring; R₄ is eachindependently a hydrogen atom; a halogen radical; or a C1-C20 alkyl oraryl radical, wherein two R₄ can be connected to form a fused ringstructure; R₃ is a C1-C20 alkyl sulfonyl, aryl sulfonyl, or silylsulfonyl radical; a C1-C20 alkyl carbonyl, aryl carbonyl, or silylcarbonyl radical; C1-C20 alkyl carboxy, or aryl carboxy radical; orC1-C20 alkyl phosphonyl, or aryl phosphonyl radical; M is a transitionmetal of Group 4; and Q₁ and Q₂ are each independently a halogenradical; a C1-C20 alkyl or aryl amido radical; a C1-C20 alkyl, alkenyl,aryl, alkylaryl, or arylalkyl radical; or a C1-C20 alkylidene radical.

In the transition metal complex of Formula 1 according to an embodimentof the present invention, a cyclopentadienyl derivative is connected toan amido group by a phenylene bridge such that a Cp—M—N angle is smallbut a Q₁—M—Q₂ angle to which a monomer approaches is large, which isillustrated in FIG. 1. In addition, compared to a CGC structure thatincludes a silicon bridge, the complex of Formula 1 has a stable, strongpentagon ring where Cp, a phenylene bridge, and nitrogen are connectedto a metal site. Accordingly, when the complex of Formula 1 which isactivated by a cocatalyst, such as methylaluminoxane, or B(C6F₅)₃, isapplied to the synthesis of polyolefin, a polyolefin with high molecularweight, and high degree of copolymerization an be obtained even at highreaction temperature. Due to such structural feature of the complex ofFormula 1, a linear low density polyethylene having a density of0.910-0.930 g/cc. In addition, since a great amount of alpha-olefin canbe comprised, a polyolefin copolymer having a very low density less than0.910 g/cc can be obtained. In addition, various substituents can beintroduced to a cyclopentadienyl ring, nitrogen, and a phenylene ring sothat electronic and steric environments in the vicinity of metal can beeasily controlled to obtain desired structure and properties of apolymer which will be formed. The transition metal complex according toan embodiment of the present invention is used to prepare a catalystthat is used to polymerize olefin monomers. However, use of thetransition metal complex is not limited thereto, that is, the transitionmetal complex can be used in any application to which the transitionmetal complex can be used.

The compound of Formula 1 may have the structure corresponding toFormula 14, which is preferred to control electronic, stericenvironments in the vicinity of metal:

where R₁₁ and R₁₂ are each independently hydrogen atom; or C1-C20 alkyl,aryl, or silyl radical;

R₁₄ is each independently hydrogen atom; a C1-C20 alkyl radical; orhalogen radical;

Q₃ and Q₄ are each independently a halogen radical; C1-C20 alkyl, oraryl amido radical; or C1-C20 alkyl radical;

M is a transition metal of Group 4; and

R₈ is

where Y is a carbon atom or a sulfur atom;

R₉ is a hydrogen atom; a C1-C20 alkyl, aryl, or silyl radical; or aC1-C20 alcoxy, or aryloxy radical; and

when Y is the carbon atom, n is 1, and when Y is the sulfur atom, n is2.

The transition metal complex of Formula 1 may be a compound of one ofthe formulae below:

where R₁₀ is a methyl radical, a tosyl radical, a mesityl radical, ort-butyl radical; Q₅ and Q₆ are each independently a methyl radical, adimethylamido radical, or a chloride radical.

Transition metal complexes according to another embodiment of thepresent invention are represented by Formulae 2 and 3 where N or G,which is a heteroatom, are bound to metal. These transition metalcomplexes may have a chemical structure of η¹-G bonding mode (Formula 2)or η²-N,G bonding mode (Formula 3), according to a substituent of acyclopentadienyl ring or phenylene bridge, or a method of synthesizing acomplex. Structures of these complexes are illustrated in FIGS. 2 and 3:

where R₁, R₂, R₄, M, Q₁ and Q₂ are described above; G is an oxygen atomor a sulfur atom; and R₅ is a hydrogen atom; a C1-C20 alkyl or arylradical; or a C1-C20 alcoxy or aryloxy radical.

where R₁, R₂, R₄, R₅, M, Q₁, and Q₂ are described above; and G′ is anoxygen atom, a sulfur atom, or a substituted nitrogen group (—NR) whereR is a C1-C20 alkyl or aryl radical. These transition metal complexesaccording to another embodiment of the present invention are used toprepare a catalyst that is used to polymerize olefin monomers. However,use of these transition metal complexes is not limited thereto, that is,the transition metal complexes can be used in any application to whichthe transition metal complex can be used.

The transition metal complex of Formula 2 or Formula 3 may have thestructure corresponding to Formula 16, which is preferred to controlelectronic, steric environments in the vicinity of metal:

where R₁₁ and R₁₂ are each independently hydrogen atom; or C1-C20 alkyl,aryl, or silyl radical;

R₁₄ is each independently a hydrogen atom; a C1-C20 alkyl radical; or ahalogen radical;

Q₃ and Q₄ are each independently a halogen radical; a C1-C20 alkyl oraryl amido radical; or a C1-C20 alkyl radical;

M and R₅ are described above; and

G″ is a oxygen atom, a sulfur atom, or a substituted nitrogen groupwhere a substituent is a C1-C20 alkyl or aryl amido radical.

The transition metal complex of Formula 2 or Formula 3 may be a compoundof any one of the formulae below:

where R₁₅ is a methyl, t-butyl, or t-butoxy radical, and Q₅ and Q₆ aredescribed above, and X is a halogen radical.

The present invention also provides amine-based compounds of Formulae 4through 7 that are ligands coordinated with metal in the transitionmetal complex of Formulae 1 through 3:

where R₁, R₂, R₃ and R₄ are described above. When these ligands arecoordinated with metal, a phenylene bridge is formed and nitrogen andcyclopentadiene are coordinated with metal. These compounds of Formulae4 through 7 may be used as a ligand of a transition metal complex.However, use of the compounds is not limited thereto. That is, thecompounds can be used in any applications.

The present invention also provides an organic ketone-based boronic acidcompound of Formula 8 that is used as an intermediate when the ligandsdescribed above are synthesized:

where R₁ and R₂ are described above.

A method of preparing transition metal complexes of Formulae 1 through 3according to an embodiment of the present invention will now bedescribed in detail. In order to obtain a novel monocyclopentadienylligand in which phenylene of Formula 4 acts as a bridge, a substitutedboronic acid is reacted with an aniline compound in the presence of Pdmetal catalyst by carbon-carbon coupling, which is Suzuki Reaction. TheSuzuki Reaction is well known in the organic chemistry to form a C—Cbond, and can be used to synthesize a monocyclopentadienyl ligand ofFormula 4 in which various substituents are introduced tocyclopentadienyl, nitrogen, and a phenylene bridge. Ultimately, thetransition metal complex of Formula 1 in which electronic and sterichindrance is controlled in the vicinity of metal can be synthesized.

Particularly, the method of synthesizing transition metal complexesrepresented by Formulae 1 through 3 includes: a) synthesizing a compoundof Formula 6 by reacting a boronic acid compound of Formula 8 with a2-bromoaniline compound of Formula 9; b) synthesizing a compound ofFormula 5 by the compound of Formula 6 with R₃X where X is a halogenatom; c) synthesizing a compound of Formula 4 by reacting a compound ofFormula 5 with R₁Li and then adding an acid thereto; and d) synthesizinga complex of Formula 1 or Formula 2 by reacting the compound of Formula4 with the compound of Formula 10 and then adding (CH₃)_(n)SiX_(4-n)where X is a halogen atom and n is 0, 1, 2, or 3 thereto:

where R₄ is described above; andM(N(R₆)₂)₄  (10)where M is a transition metal of Group 4, and

R₆ is a C1-C20 alkyl or aryl radical.

In operation (a), the boronic acid compound of Formula 8 can be obtainedby reacting an unsaturated keton compound with a boron triester compoundin a solvent of THF or ether and then adding an acid thereto, and theboronic acid compound of Formula 8 is reacted with a bromoanilinecompound in the presence of a palladium catalyst via Suzuki Couplingreaction to form an amine-based compound of Formula 6. The palladiumcatalyst used can be a phosphine-based complex of Formula 11 which iswell known. For example, the palladium catalyst istetrakis(triphenylphosphine)palladium.

where R is alkyl or aryl; and X is a halogen atom.

In operation (b), a compound of Formula 6 is reacted with R₃—X where Xis a halogen atom in the presence of an amine-based base, such aspylidine or triethylamine so that an acid such as H—X is removed and acompound of Formula 5 can be obtained. In the R₃—X, R₃ is selected froma C1-C20 alkyl sulfonyl or aryl sulfonyl radical, a C1-C20 alkylcarbonyl or aryl carbonyl radical, a C1-C20 alkyl carboxy or arylcarboxy radical, and a C1-C20 alkyl phosphonyl or aryl phosphonylradical, and is preferably selected from methylsulfonyl,toluenesulfonyl, mesitylsulfonyl, and t-butylcarbonyl.

In operation (c), a compound of Formula 5 is reacted with an R₁Licompound at low temperature and then an acid treatment is performed,thereby obtaining a compound of Formula 4. In order to increase thereactivity of the R₁Li compound, the R₁Li compound can be used togetherwith a metal Lewis acid such as CeCl₃. In the R₁Li compound, R₁ isselected from a C1-C20 alkyl or aryl; a C1-C20 alkenyl, alkylaryl, orarylalkyl; and a metalloid radical of Group 14 metal substituted withhydrocarbyl, preferably is a C1-C10 alkyl or aryl radical, and morepreferably is selected from methyl, t-butyl, phenyl, benzyl, and(trimethyl)silylmethyl.

In operation (d), the monocyclopentadienyl ligand of Formula 4 preparedabove is reacted with a Group 4 metal amino compound of Formula 10, andthen (CH₃)_(n)SiX_(4-n) where X is halogen and n is 0, 2, or 3 is addedthereto, thereby obtaining Group 4 transition metal complexes ofFormulae 1 through 3 according to the ligand structure change. The Group4 metal amino compound is selected from tetrakis(dimethylamino)titanium,tetrakis(diethylamino)titanium, tetrakis(dimethylamino)zirconium,tetrakis(diethylamino)zirconium, tetrakis(dimethylamino)hafnium, andtetrakis(diethylamino)hafnium, and preferably selected fromtetrakis(dimethylamino)titanium, tetrakis(dimethylamino)zirconium, andtetrakis(dimethylamino)hafnium. The reaction temperature of themonocyclopentadienyl ligand with the Group 4 metal amino compound may bein the range of 30° C.-150° C., preferably 50° C.-120° C., and morepreferably 50° C.-100° C. The reaction time of the monocyclopentadienylligand with the Group 4 metal amino compound may be in the range of6-168 hours, preferably 10-72 hours, and more preferably 12-48 hours.When the reaction temperature is less than 30° C., the ligand isinsufficiently reacted with the metal amino compound and thus the yieldand purity of the reaction product decrease. When the reactiontemperature is higher than 150° C., the reaction product is thermallyunstable and thus the yield and purity of the reaction productdecreases. When the reaction time is shorter than 6 hours, the ligand isinsufficiently reacted with the metal amino compound, whereas when thereaction time is longer than 168 hours, the obtained products may bechanged into a different metal compound. In operation (d), the silanecompound may be selected from chlorotrimethylsilane,dichlorodimethylsilane, trichloromethylsilane, and tetrachlorosilane.The mol ratio of the Group 4 metal compound that will react to thesilane compound may be in the range of 1:1 to 1:5, and preferably 1:2 to1:3. When the mol ratio of the Group 4 metal compound to the silanecompound is less than 1:1, the chloride substitution occursinsufficiently and thus the yield and purity of the product decrease. Onthe other hand, when the mol ratio of the Group 4 metal compound to thesilane compound is greater than 1:5, the obtained product can be changedinto a different metal compound due to excess silane compound. In thiscase, however, excess silane compound may not affect significantly.

A method of preparing transition metal complexes of Formulae 1 through 3according to another embodiment of the present invention includes: (a)synthesizing a compound of Formula 6 by reacting a boronic acid compoundof Formula 8 with a 2-bromoaniline compound of Formula 9; (b)synthesizing a compound of Formula 7 by the compound of Formula 6 withR₁Li and then adding an acid thereto; (c) synthesizing a compound ofFormula 4 by reacting a compound of Formula 7 with R₃X where X is ahalogen atom; and (d) synthesizing a complex of Formula 1 or Formula 2by reacting the compound of Formula 4 with the compound of Formula 10and then adding (CH₃)_(n)SiX_(4-n) where X is a halogen atom and n is 0,1, 2, or 3 thereto. The present method is the same as the previousmethod, except that operation b and operation c of the previous methodcorrespond to operation c′ and operation b′ of the present method,respectively. Respective operations of the present method is the same asin the previous method.

Methods of synthesizing the complexe of Formula 1 may be represented byReaction Scheme 1 or Reaction Scheme 2:

These Reaction Schemes can also be used to the complexes of Formula 2,and Formula 3.

Meanwhile, the complex of Formula 3 can be synthesized using othermethods. For example, a method of synthesizing the complex of Formula 3includes: e) synthesizing a dilithium form of the compound of Formula 7by reacting a compound of Formula 7 with an alkyllithium that is a base;and f) synthesizing a complex of Formula 3 by reacting an in-situmixtures composed of the dilithium compound, alkyllithium and MX₄ whereX is halogen and M is a transition metal of Group 4, which isrepresented by Reaction Scheme 3:

The Group 4 transition metal complex of Formula 3 can be easilysynthesized using the method represented by Reaction Scheme 3, not usingthe Group 4 transition metal complex of Formula 10 and the siliconcompound in operation (d) of the methods of synthesizing the complexesof Formula 1 through Formula 3. According to operation (e) of ReactionScheme 3, in the presence of THF or diethylether, the ligand of Formula7 is reacted with 2 eq. n-BuLi that is a strong base, thereby forming adilithiated solid compound. According to operation (f), at a lowtemperature of −78° C., a Group 4 metal tetrachloride is reacted with 2eq. alkyllithium compound, such as MeLi, thereby formingMe₂MCl₂(solvent)_(n) where M is Ti or Zr, a solvent is THF or Et₂O, n is1 or 2. And, the dilithium salt compound prepared in operation (e)reacts in-situ with the Me₂MCl₂(solvent)_(n) to obtain the complex ofFormula 3. When this method is used, the complex of Formula 3, inparticular, a complex of Formula 3 where Q₁ and Q₂ are directlysubstituted with alkyl or aryl group can be obtained with a large yield(70% or more).

A catalyst composition according to an embodiment of the presentinvention including: a complex of one of Formulae 1 through 3, and atleast one cocatalyst selected from compounds of Formula 11 through 13.The catalyst composition can be used for homopolymerization orcopolymerization of olefin:—[Al(R₇)—O]_(a)—  (11)where R₇ is each independently a halogen radical; a C1-C20 hydrocarbylradical; or a C1-C20 hydrocarbyl radical substituted with halogen, a isan integer of 2 or greater;D(R₇)₃  (12)where D is aluminum or boron, R₇ is described above; and[L—H]⁺[Z(A)₄]⁻, or [L]⁺[Z(A)₄]⁻  (13)where L is a neutral or cationic Lewis acid, H is a hydrogen atom; Z isan element of Group 13; and A is each independently a C6-C20 aryl oralkyl radical in which at least one hydrogen atom is substituted withhalogen or a C1-C20 hydrocarbyl, alkoxy, or penoxy radical.

A method of preparing the catalyst composition according to anembodiment of the present invention include contacting the transitionmetal complex with the compound of Formula 11 or Formula 12 to obtain amixture, and adding a compound of Formula 13 to the mixture. A method ofpreparing the catalyst composition according to another embodiment ofthe present invention includes contacting the transition metal complexwith the compound of Formula 11.

In the former method of preparing a catalyst composition, the mole ratioof the transition metal complex to the compound of Formula 11 or Formula12 may be in the range of 1:2 to 1:5,000, preferably 1:10 to 1:1,000,and preferably 1:20 to 1:500, and the mole ratio of the transition metalcomplex to the compound of Formula 13 may be in the range of 1:1 to1:25, preferably 1:1 to 1:10, and most preferably 1:2 to 1:5. When themole ratio of the transition metal complex to the compound of Formula 11or Formula 12 is less than 1:2, the amount of the alkylating agent is sosmall that the metal compound is insufficiently alkylated. On the otherhand, the mole ratio of the transition metal complex to the compound ofFormula 11 or Formula 12 is greater than 1:5,000, the metal compound isalkylated, but excess alkylating agent can react with the activator ofFormula 13 so that the alkylated metal compound is less activated. Whenthe mole ratio of the transition metal complex to the compound ofFormula 13 is less than 1:1, the amount of the activator is relativelysmall so that the metal compound is less activated. On the other hand,when the ratio of the transition metal complex to the compound ofFormula 13 is greater than 1:25, the metal compound may be completelyactivated but excess activator remains, that is, the preparation processfor the catalyst composition is expensive, and the obtained polymerpurity is poor.

In the latter method of preparing the catalyst composition, the molratio of the transition metal complex to the compound of Formula 11 maybe in the range of 1:10 to 1:10,000, preferably 1:100 to 1:5,000, andmost preferably 1:500 to 1:2,000. When the mole ratio of the transitionmetal complex to the compound of Formula 11 is less than 1:10, theamount of the compound of Formula 11 is relatively small so that thetransition metal complex is less activated and the obtained catalystcomposition has low activity. On the other hand, when the mole ratio ofthe transition metal complex to the compound of Formula 11 is greaterthan 1:10,000, the metal compound is completely activated but excessactivator remains, that is, the preparation process for the catalystcomposition is expensive, and the obtained polymer purity is poor.

The reaction solvent used to preparing the activated catalystcomposition can be a hydrocarbon based solvent, such as pentane, hexane,and heptane, or an aromatic solvent, such as benzene and toluene. Thetransition metal complexes of Formulae 1 through 3 and the cocatalystscan be supported by silica or alumina for use.

Examples of the compound of Formula 11 may include methylaluminoxane,ethylaluminoxane, isobutylaluminoxane, butylaluminoxane etc. For examplethe compound of Formula 11 is methylaluminoxane.

Examples of the alkyl metal compound of Formula 12 may includetrimethylaluminum, triethylaluminum, triisobutylaluminum,tripropylaluminum, tributylaluminum, dimethylchloroaluminum,triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum,tripentylaluminum, triisopentylaluminum, trihexylaluminum,trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum,triphenylaluminum, tri-p-tolylaluminum, dimethylaluminummethoxide,dimethylaluminmethoxide, trimethylboron, triethylboron,triisobutylboron, tripropylboron, tributylboron etc. For example, thealkyl metal compound of Formula 12 is trimethylaluminum,triethylaluminum, or triisobutylaluminum.

Examples of the compound of Formula 13 may includetriethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron,trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron,trimethylammoniumtetra(p-tolyl)boron,trimethylammoniumtetra(o,p-dimethylphenyl)boron,tributylammoniumtetra(p-trifluoromethylphenyl)boron,trimethylammoniumtetra(p-trifluoromethylphenyl)boron,tributylammoniumtetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetraphenylboron,N,N-diethylaniliniumtetrapentafluorophenylboron,diethylammoniumtetrapentafluorophenylboron,triphenylphosphoniumtetraphenyl boron,trimethylphosphoniumtetraphenylboron,triethylammoniumtetraphenylaluminum,tributylammoniumtetraphenylaluminum,trimethylammoniumtetraphenylaluminum,tripropylammoniumtetraphenylaluminum,trimethylammoniumtetra(p-tolyl)aluminum,tripropylammoniumtetra(p-tolyl)aluminum,triethylammoniumtetra(o,p-dimethylphenyl)aluminum,tributylammoniumtetra(p-trifluoromethylphenyl)aluminum,trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum,tributylammoniumtetrapentafluorophenylaluminum,N,N-diethylaniliniumtetraphenylaluminum,N,N-diethylaniliniumtetraphenylaluminum,N,N-diethylaniliniumtetrapentafluorophenylaluminum,diethylammoniumtetrapentatetraphenylaluminum,triphenylphosphoniumtetraphenylaluminum,trimethylphosphoniumtetraphenylaluminum,triethylammoniumtetraphenylaluminum,tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylboron,tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron,tripropylamoniumtetra(p-tolyl)boron,triethylammoniumtetra(o,p-dimethylphenyl)boron,trimethylammoniumtetra(o,p-dimethylphenyl)boron,tributylammoniumtetra(p-trifluoromethylphenyl)boron,trimethylammoniumtetra(p-trifluoromethylphenyl)boron,tributylammoniumtetrapentafluorophenylboron,N,N-diethylaniliniumtetraphenylboron,N,N-diethylaniliniumtetraphenylboron,N,N-diethylaniliniumtetrapentafluorophenylboron,diethylammoniumtetrapentafluorophenylboron,triphenylphosphoniumtetraphenylboron,triphenylcarboniumtetra(p-trifluoromethylphenyl)boron,triphenylcarboniumtetrapentafluorophenylboron etc.

A method of preparing a homopolymer or copolymer of polyolefin accordingto an embodiment of the present invention includes contacting a catalystcomposition that contains the complex of one of Formulae 1 through 3 andat least one compound selected from compounds of Formulae 11 through 13with at least one olefin monomer.

A polymerization process using the catalyst composition may be asolution process, but when the catalyst composition is used togetherwith an inorganic support, such as silica, the polymerization processcan also be a slurry or vapor process.

The catalyst composition can be melted or diluted in a solvent suitablefor olefin polymerization, before being used. The solvent can be aC5-C12 aliphatic hydrocarbon solvent, such as pentane, hexane, heptane,nonane, decane, or isomers of these; an aromatic hydrocarbon, such astoluene or benzene; or a hydrocarbon solvent that is substituted with achloride atom, such as dichloromethane or chlorobenzene. The solventused therein may be treated with a small amount of alkylaluminum toremove water or air, which acts as a catalyst poison. When needed, morecocatalysts such as alkylaluminium can be used for the same purpose.

Examples of an olefin based monomer that can be polymerized using themetal complexes and the cocatalysts may include ethylene, alpha-olefin,cyclic olefin etc. In addition, a diene or triene olefin-based monomerhaving at least two double bonds can be polymerized. In particular, theolefin-based monomer can be ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene,norbonadiene, ethyllidenenorbonene, phenylnorbonene, vinylnorbonene,dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene,stylene, alpha-methylstylene, divinylbenzene, or 3-chloromethylstylene.In addition, at least two different monomers of these can becopolymerized. The catalyst composition according to an embodiment ofthe present invention is used to copolymerize ethylene and 1-octenehaving large steric hindrance at a high reaction temperature of 90° C.to thereby obtain a copolymer having high molecular weight but having avery low density less than 0.910 g/cc.

A monomer of the copolymer may include ethylene and at least onecompound selected from propylene, 1-butene, 1-hexene, and4-methyl-1-pentene, and 1-octene.

The present invention will be described in further detail with referenceto the following examples. These examples are for illustrative purposesonly and are not intended to limit the scope of the present invention.

Synthesis of Ligand and Metal Complex

Organic reagents and solvents were obtained from Aldrich Co., Inc. andMerck Co., Inc. and purified using a standard method. Each process forthe synthesis was performed being isolated from air and moisture toimprove reproducibility of experiments. The structure of compounds wasidentified using a 400 MHz nuclear magnetic resonance (NMR) and an X-rayspectrometer.

EXAMPLE 1 2-dihydroxyboryl-3-methyl-2-cyclopenten-1-one

44.80 g (204.49 mmol) of 2-bromo-3-methyl-2-cyclopenten-1-on ethyleneketal compound were mixed with 240 mL of THF, and then 82 mL(204.49mmol) of n-BuLi (2.5M in hexane) was added thereto at −78° C. Theresultant mixture was mixed at −78° C. for one hour. Then, 42.31 g(224.95 mmol) of boron triisopropylester was added to the reactionproduct and then mixed at −60° C. or less for one hour. The resultantmixture was further reacted at −50° C. for 30 minutes, and then 110 mLof 2 N HCl was added thereto and mixed for 10 minutes. Subsequently, thereaction product was loaded to a separating funnel, 200 mL ofethylacetate (E.A) was added thereto, and then an organic layer wasextracted therefrom. 55 mL of ethyl acetate (E.A) was used twice toextract the organic layer. The collected organic layer was dried overMgSO₄ to remove water therein and filtered using a glass filter. Thesolvent contained in the dried product was removed using a rotary vacuumevaporator to obtain a solid product. The solid product was melted using300 mL of E.A and then twice recrystallized at −30° C. The remainingorganic layer was column chromatographed (hexane:E.A=1:1) to removeby-products, and then recrystallized (24.30 g, 85%)

¹H NMR (CDCl₃): =6.75(s, 2H, OH), 2.69-2.67 (m, 2H, CH₂), 2.51-2.49 (m,2H, CH₂), 2.45 (s, 3H, CH₃); ¹³C {¹H} NMR (CDCl₃): =217.35, 193.42,35.73, 35.12, 20.42

EXAMPLE 2 2-dihydroxyboryl-3,4-dimethyl-2-cyclopenten-1-one

2-dihydroxyboryl-3,4-dimethyl-2-cyclopenten-1-one was obtained in thesame manner as in Example 1 using2-bromo-3,4-dimethyl-2-cyclopenten-1-one ethylene ketal compound (86%).

¹H NMR (CDCl₃): δ 1.24 (d, J=3.6 Hz, 3H, CH₃), 2.09 (dd, J=19, 2.0 Hz,1H, CH₂), 2.39 (s, 3H, CH₃), 2.72 (dd, J=19, 6.8 Hz, 1H, CH₂), 2.84-2.86(m, 1H, CH), 7.29 (s, 2H, OH) ppm. ¹³C{¹H} NMR (CDCl₃): δ 18.01, 18.90,40.76, 44.22, 197.08, 216.12 ppm.

EXAMPLE 3 2-(2-aminophenyl)-3-methyl-2-cyclopenten-1-one

4.00 g (28.584 mmol) of 2-dihydroxyboryl-3-methyl-2-cyclopenten-1-onecompound, 0.30 g (0.260 mmol) of tetrakis(triphenylphosphine)palladium,4.13 g (38.978 mmol) of sodium carbonate were loaded to 250 mL schlenkflask, and then 80 mL of degassing DME and 27 mL of H₂O that had beenpurged with N₂ were added thereto using a syringe. 4.47 g (25.985 mmol)of 2-bromoaniline was added to the flask using a syringe and reacted at90° C. for 12 hours.

Subsequently, the reaction product, 200 mL of ethylacetate, and 100 mLof H₂O were added to a separating funnel. Then, the organic layer wasextracted. Subsequently, 100 mL of ethylacetate was added to the aqueousliquid to extract an organic layer again. The organic layer was driedover MgSO₄ to remove water therein and then a rotary vacuum evaporatorwas used to remove the remaining solvent. Then, the resultant organiclayer was column chromatographed (hexane:E.A=1:1) (3.55 g, 73%).

¹H NMR (CDCl₃): =7.12 (td, J=7.6 Hz, 1H, Ph), 6.89 (dd, J=7.6 Hz, 1H,Ph), 6.77 (td, J=7.6 Hz, 1H, Ph), 6.72 (dd, J=7.6 Hz, 1H, Ph), 3.72 (brs, 2H, NH₂), 2.71-2.68 (m, 2H, CH₂CP), 2.56-2.54 (m, 2H, CH₂CP), 2.08(s, 3H, CH₃); ¹³C {¹H} NMR (CDCl₃): =207.84, 174.84, 144.60, 139.42,130.44, 128.73, 118.13, 117.84, 116.30, 34.74, 32.13, 18.56

EXAMPLE 4 2-(2-amino-4-fluorophenyl)-3-methyl-2-cyclopenten-1-one

4.937 g (25.982 mmol) of 2-bromo-4-fluoroaniline, 4.00 g (28.584 mmol)of 5-methyl-1-cyclopenten-2-one boronic acid compound, 0.30 g (0.260mmol) of tetrakis(triphenylphosphine)palladium, and 4.13 g (38.978 mmol)of sodium carbonate were loaded to 250 mL schlenk flask, and then 80 mLof degassing DME and 27 mL of H₂O that had been purged with N₂ wereadded thereto using a syringe. The mixture was reacted at 90° C. for 12hours. The work-up was the same as in Example 3 (3.84 g, 72%).

¹H NMR (CDCl₃): =6.83 (t, J=7.6 Hz, 1H, Ph), 6.48 (t, J=7.6 Hz, 1H, Ph),6.43 (d, J=10.4 Hz, 1H, Ph), 3.82 (br s, 2H, NH₂), 2.73-2.71 (m, 2H,CH₂CP), 2.58-2.55 (m, 2H, CH₂ ^(Cp)), 2.09 (s, 3H, CH₃); ¹³C {¹H} NMR(CDCl₃): =207.93, 175.26, 168.18(d, J=242.6 Hz, PhC-F) 146.47(d, J=5.7Hz, Ph), 138.76, 131.90(d, J=9.8 Hz, Ph), 113.71, 105.08(d, 22 Hz, Ph),102.91 (d, 22 Hz, Ph), 34.79, 32.22, 18.63

EXAMPLE 5 2-(2-amino-5-fluorophenyl)-3-methyl-2-cyclopenten-1-one

4.46 g (21.44 mmol) of 2-bromo-4-fluoroaniline, 3.30 g (23.582 mmol) of5-methyl-1-cyclopenten-2-one boronic acid compound, 0.204 g (0.177 mmol)of tetrakis(triphenylphosphine)palladium, and 3.41 g (32.173 mmol) ofsodium carbonate were loaded to 250 mL schlenk flask, and then 66 mL ofdegassing DME and 22 mL of H₂O that had been purged with N₂ were addedthereto using a syringe. The mixture was reacted at 90° C. for 12 hours.The work-up was the same as in Example 3 (3.76 g, 79%).

¹H NMR (CDCl₃): =6.74(td, J=8.8 Hz, 1H, Ph), 6.45 (d, J=7.6 Hz, 1H, Ph),3.65 (br s, 2H, NH₂), 2.71-2.69 (m, 2H, CH₂ ^(Cp)), 2.54-2.52 (m, 2H,CH₂CP), 2.07 (s, 3H, CH₃); ¹³C {¹H} NMR (CDCl₃): =207.05, 176.05,155.17(d, J=12.9 Hz, Ph), 152.63 (dd, J=12.9 Hz, Ph), 150.11 (d, J=12.9Hz, Ph), 137.79, 129.60(d, J=3.1 Hz, Ph), 120.43 (dd, J=12.9 Hz, Ph),111.97 (dd, 1.8 Hz, 22 Hz, Ph), 103.00 (t, 22 Hz, Ph), 34.66, 32.28,18.50

EXAMPLE 6 2-(2-amino-5-methylphenyl)-3-methyl-2-cyclopenten-1-one

1.607 g (8.031 mmol) of 2-bromo-4-methylaniline, 1.180 g (8.432 mmol) of5-methyl-1-cyclopenten-2-one boronic acid compound, 0.093 g (0.080 mmol)of tetrakis(triphenylphosphine)palladium, and 1.277 g (12.047 mmol) ofsodium carbonate were loaded to 250 mL schlenk flask, and then 24 mL ofdegassing DME and 8 mL of H₂O that had been purged with N₂ were addedthereto using a syringe. The mixture was reacted at 90° C. for 12 hours.The work-up was the same as in Example 3 (1.66 g, 96%).

¹H NMR (CDCl₃): =6.88(s, 1H, Ph), 6.60 (s, 1H, Ph), 3.49 (br s, 2H,NH₂), 2.74 ?? 2.72(m, 2H, CH₂ ^(Cp)), 2.60??2.58(m, 2H, CH₂ ^(Cp)), 2.24(s, 3H, CH₃), 2.19 (s, 3H, CH₃), 2.10 (s, 3H, CH₃); ¹³C {¹H} NMR(CDCl₃): =207.97, 174.68, 140.18, 139.97, 131.04, 128.58, 126.96,123.00, 117.56, 34.93, 32.19, 20.48, 18.71, 17.89

EXAMPLE 72-(2-(2-mesitylenesulfonyl)aminophenyl)-3-methyl-2-cyclopenten-1-one

0.500 g (2.67 mmol) of 2-(2-aminophenyl)-3-methyl-2-cyclopenten-1-one,0.253 g (3.204 mmol) of pyridine, 0.584 g (2.67 mmol) of2-mesitylenesulfonyl chloride), and 2 mL of M.C (methylene chloride)were loaded to a 20 mL vial, and then reacted for 12 hours. 10 mL of M.Cand 4 mL of 2 N HCl were added to the reaction product. The resultantorganic layer is collected and then dried over MgSO₄ to remove water.The solvent contained in the dried product was removed using a rotaryvacuum evaporator. The obtained solid was washed with 10 mL of diethylether and filtered using a glass filter. The filtered product was driedin vacuum to remove the solvent that had remained therein (0.790 g,80%).

¹H NMR (CDCl₃): =7.51(d, J=7.6 Hz, 1H, Ph), 7.22 (t, J=7.6 Hz, 1H, Ph),7.07 (t, J=7.6 Hz, 1H, Ph), 6.96 (d, J=7.6 Hz, 1H, Ph), 6.83 (s, 2H,Ph^(Mes)), 6.77 (s, 1H, NH), 2.44-2.40 (m, 4H, CH₂*2), 2.42 (s, 6H,Ph^(Mes)), 2.36 (s, 3H, Ph^(Mes)), 1.76 (s, 3H, CH₃).

EXAMPLE 82-(2-(2-mesitylenesulfonyl)amino-4-fluorophenyl)-3-methyl-2-cyclopenten-1-one

0.800 g (3.90 mmol) of2-(2-amino-4-fluorophenyl)-3-methyl-2-cyclopenten-1-one, 0.339 g (4.29mmol) of pyridine, 0.938 g (4.29 mmol) of 2-mesitylenesulfonyl chloride,and 4 mL of M.C were loaded to a 20 mL vial, and then reacted for 12hours. The work-up was the same as in Example 7 (1.29 g, 85%).

¹H NMR (CDCl₃): =7.84(s, 1H, NH), 7.19 (d, J=6.0 Hz, 1H, Ph), 6.90 (m,2H, Ph), 6.84 (s, 2H, Ph^(Mes)), 2.54-2.46 (m, 4H, CH₂ ^(Cp)*2), 2.09(s, 3H, CH₃), 2.39 (s, 6H, Ph^(Mes)), 2.28 (s, 3H, Ph^(Mes)), 1.80 (s,3H, CH₃); ¹³C {¹H} NMR (CDCl₃): =208.89, 177.35, 163.41, 160.93, 141.81,139.72, 138.26, 136.26, 134.87, 131.79, 131.72, 123.23, 114.95, 113.20,34.63, 32.81, 23.31, 20.92, 18.57

EXAMPLE 92-(2-(2-mesitylenesulfonyl)amino-5-fluorophenyl)-3-methyl-2-cyclopenten-1-one

0.700 g (3.14 mmol) of2-(2-amino-5-fluorophenyl)-3-methyl-2-cyclopenten-1-one, 0.273 g (3.45mmol) of pyridine, 0.754 g (3.45 mmol) of 2-mesitylenesulfonyl chloride,and 3 mL of M.C were loaded to a 20 mL vial, and then reacted for 12hours. The work-up was the same as in Example 7 (0.760 g, 60%).

¹H NMR (CDCl₃): =7.05(s, 1H, NH), 6.90 (s, 1H, Ph), 6.87 (s, 2H,Ph^(Mes)), 6.54 (d, J=7.6 Hz, 1H, Ph), 2.54-2.46 (m, 4H, CH₂ ^(Cp)*2),2.42 (s, 6H, CH₃Ph^(Mes)), 2.31 (s, 3H, CH₃), 2.01 (s, 3H, CH₃); ¹³C{¹H} NMR (CDCl₃): =207.55, 177.49, 162.06, 159.63, 159.10, 141.71,138.76, 137.87, 135.55, 133.99, 131.67, 112.72, 104.67, 34.70, 32.84,23.40, 21.02, 18.83

EXAMPLE 102-(2-(2-mesitylenesulfonyl)amino-5-methylphenyl)-3-methyl-2-cyclopenten-1-one

0.700 g (3.25 mmol) of2-(2-amino-5-methylphenyl)-3-methyl-2-cyclopenten-1-one, 0.283 g (3.58mmol) of pyridine, 0.782 g (3.58 mmol) of 2-mesitylenesulfonyl chloride,and 3 mL of M.C were loaded to a 20 mL vial, and then reacted for 12hours. The work-up was the same as in Example 7 (1.29 g, 85%).

¹H NMR (CDCl₃): =7.24(s, 1H, NH), 7.01 (s, 1H, Ph), 6.76 (s, 2H,Ph^(Mes)), 6.48 (s, 1H, Ph), 2.43-2.39 (m, 4H, CH₂ ^(Cp)*2), 2.41 (s,3H, CH₃), 2.36 (s, 6H, Ph^(Mes)), 2.25 (s, 6H, PhCH₃*2), 1.92 (s, 3H,Ph^(Mes)); ¹³C {¹H} NMR (CDCl₃): =207.97, 174.68, 140.18, 139.97,132.24, 131.58, 131.04, 130.15, 129.57, 128.58, 126.96, 123.00, 117.56,34.93, 32.19, 23.09 20.48, 19.89, 18.71, 17.89

EXAMPLE 112-(2-(p-toluenesulfonyl)aminophenyl)-3-methyl-2-cyclopenten-1-one

0.815 g (4.35 mmol) of 2-(2-aminophenyl)-3-methyl-2-cyclopenten-1-one,pyridine 0.413 g (5.22 mmol), 0.829 g (5.22 mmol) of p-toluenesulfonylchloride, and 4 mL of M.C were loaded to a 20 mL vial, and then reactedfor 12 hours. The work-up was the same as in Example 7 (1.330 g, 89%).

¹H NMR (CDCl₃): =7.80(s, 1H, NH), 7.55 (d, 1H, Ph), 7.43 (d, J=8.0 Hz,2H, Ph^(Ts)), 7.33 (t, 1H, Ph), 7.19 (t, 1H, Ph), 7.12 (d, J=8.0 Hz, 2H,Ph^(Ts)), 6.89 (d, 1H, Ph), 2.43-2.40 (m, 4H, CH₂ ^(Cp)*2), 2.36 (s, 3H,CH₃), 1.75 (s, 3H, CH₃); ¹³C {¹H} NMR (CDCl₃): =208.91, 177.40, 142.75,138.71, 137.33, 134.29, 130.62, 129.09, 129.00, 127.78, 127.04, 126.52,126.13, 34.52, 32.61, 21.42, 18.76

EXAMPLE 122-(2-(p-toluenesulfonyl)amino-5-fluorophenyl)-3-methyl-2-cyclopenten-1-one

0.700 g (3.14 mmol) of2-(2-amino-5-fluorophenyl)-3-methyl-2-cyclopenten-1-one, 0.298 g (3.76mmol) of pyridine, 0.598 g (3.76 mmol) of p-toluenesulfonyl chloride,and 3 mL of M.C were loaded to a 20 mL vial, and then reacted for 12hours. The work-up was the same as in Example 7 (1.000 g, 85%).

¹H NMR (CDCl₃): =7.62(s, 1H, NH), 7.52 (s, 1H, Ph), 7.38 (d, J=8.0 Hz,2H, Ph^(Ts)), 7.28 (s, 1H, Ph), 7.06 (d, J=8.0 Hz, 2H, Ph^(Ts)),2.39-2.35 (m, 4H, CH₂ ^(Cp)*2), 2.25 (s, 3H, CH₃), 1.69 (s, 3H, CH₃);¹³C {¹H} NMR (CDCl₃): =207.56, 175.29, 141.94, 138.54, 136.27, 134.38,130.62, 128.95, 128.57, 127.57, 126.96, 126.43, 125.93, 34.54, 33.08,22.06, 17.91

EXAMPLE 132-(2-(p-toluenesulfonyl)amino-5-methylphenyl)-3-methyl-2-cyclopenten-1-one

0.600 g (2.79 mmol) of2-(2-amino-5-methylphenyl)-3-methyl-2-cyclopenten-1-one, 0.243 g (3.07mmol) f pyridine, 0.858 g (3.07 mmol) of p-toluenesulfonyl chloride, and3 mL of M.C were loaded to a 20 mL vial, and then reacted for 12 hours.The work-up was the same as in Example 7 (0.800 g, 78%).

¹H NMR (CDCl₃): =7.28(s, 1H, NH), 7.21 (d, J=8.0 Hz, 2H, Ph^(Ts)), 7.14(s, 1H, Ph), 6.76 (d, J=8.0 Hz, 2H, Ph^(Ts)), 6.86 (s, 1H, Ph),2.43-2.39 (m, 4H, CH₂ ^(Cp)*2), 2.41 (s, 3H, CH₃), 2.25 (s, 6H,PhCH₃*2), 1.92 (s, 3H, Ph^(Ts)); ¹³C {¹H} NMR (CDCl₃): =208.95, 172.54,139.54, 139.95, 132.24, 131.58, 130.84, 130.55, 129.52, 129.47, 128.96,122.84, 116.52, 34.85, 31.94, 22.86 20.25, 19.67, 17.57

EXAMPLE 14 2-(2-amino)phenyl-3,4-dimethyl-2-cyclopenten-1-one

Yellow oil was obtained in the same manner as in Example 3, using 4.000g (25.984 mmol) of 2-dihydroxyboryl-3,4-dimethyl-2-cyclopenten-1-one,3.443 g (32.497 mmol) of sodium carbonate, 0.751 g (0.650 mmol) oftetrakis(triphenylphosphine)palladium, and 3.725 g (21.653 mmol) of2-bromoaniline (2.872 g, 66%).

¹H NMR (CDCl₃): δ 1.32(d, J=3.6 Hz, 3H, CH₃), 2.07 (s, 3H, CH₃), 2.19(dd, J=18.4, 1.6 Hz, 1H, CH₂—H), 2.83 (dd, J=18.4, 6.4 Hz, 1H, CH₂—H),2.86 (qd, J=6.4, 1.6 Hz, 1H, CH—H), 3.72 (br s, 2H, NH₂), 6.77 (dd,J=7.6, 1.6 Hz, 1H, Ph), 6.81 (td, J=7.6, 1.6 Hz, 1H, Ph), 6.91 (dd,J=7.6, 1.6 Hz, 1H, Ph), 7.15 (td, J=7.6, 1.6 Hz, 1H, Ph) ppm. ¹³C{¹H}NMR (CDCl₃): δ 16.39, 19.39, 37.97, 43.51, 116.60, 117.01, 118.16,118.55, 128.97, 130.67, 144.45, 178.93, 207.02 ppm.

EXAMPLE 152-(2-amino-3,5-dimethyl)phenyl-3,4-dimethyl-2-cyclopenten-1-one

White solid was obtained in the same manner as in Example 3, using 3.459g (22.465 mmol) of 2-dihydroxyboryl-3,4-dimethyl-2-cyclopenten-1-one,2.976 g (28.076 mmol) of sodium carbonate, 0.649 g (0.562 mmol) oftetrakis(triphenylphosphine)palladium, and 3.745 g (18.718 mmol) of2-bromo-4,6-dimethylaniline (3.161 g, 74%).

¹H NMR (CDCl₃): δ 1.32(d, J=3.6 Hz, 3H, CH₃), 2.04 (s, 3H, CH₃), 2.18(s, 3H, CH₃), 2.20 (s, 1H, CH₂—H), 2.24 (s, 3H, CH₃), 2.82 (dd, J=18.4,6.4 Hz, 1H, CH₂—H), 2.94 (qd, J=6.4, 1.6 Hz, 1H, CH—H), 3.48 (br s, 2H,NH₂), 6.60 (s, 1H, Ph), 6.88 (s, 1H, Ph) ppm. ¹³C{¹H} NMR (CDCl₃): δ16.19, 17.76, 19.32, 20.37, 37.67, 43.45, 117.42, 122.79, 126.74,128.44, 130.88, 140.02, 178.58, 106.85 ppm.

EXAMPLE 162-(2-amino-3,5-difluoro)phenyl-3,4-dimethyl-2-cyclopenten-1-one

White solid was obtained in the same manner as in Example 3, using 2.000g (12.990 mmol) of 2-dihydroxyboryl-3,4-dimethyl-2-cyclopenten-1-one,1.967 g (18.557 mmol) of sodium carbonate, 0.429 g (0.371 mmol) oftetrakis(triphenylphosphine)palladium, and 2.436 g (12.371 mmol) of2-bromo-4,6-difluoroaniline (1.938 g, 76%).

¹H NMR (CDCl₃): δ 1.29(d, J=3.6 Hz, 3H, CH₃), 2.04 (s, 3H, CH₃), 2.15(dd, J=18.8, 2.0 Hz, 1H, CH₂—H), 2.79 (dd, J=18.8, 14.4 Hz, 1H, CH₂—H),2.93 (q, J=6.4 Hz, 1H, CH—H), 3.65 (br s, 2H, NH₂), 6.54 (d, J_(H-F)=8.8Hz, 1H, Ph), 6.78 (t, J_(H-F)=8.8 Hz, 1H, Ph) ppm.

EXAMPLE 172-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(2-mesitylenesulfonyl)amine

0.645 g (1.746 mmol) of2-(2-(2-mesitylenesulfonyl)aminophenyl)-3-methyl-2-cyclopenten-1-one and12 mL of THF were loaded to a 50 mL flask, and then 2.30 mL (3.677 mmol)of MeLi (1.6 M in diethyl ether) was added thereto at −78° C. andstirred at the same temperature for two hours. The reaction product wasstirred for 2 hours while the temperature was slowly raised. 10 mL ofdistilled water was added to the resultant reaction product and the THFcontained therein was removed using a rotary vacuum evaporator. 10 mL ofE.A and 5 mL of 2 N HCl were added to the reaction product from whichthe THF had been removed and strongly stirred for 3 minutes.Subsequently, the organic layer was collected from the stirred reactionproduct. 5 mL of E.A was twice added to the aqueous layer to obtain theorganic layer. The collected organic layer was neutralized using 5 mL ofNaHCO₃ and dried over MgSO₄ to remove water contained therein. Thesolvent contained in the dried product was removed using a rotary vacuumevaporator. The product was filtered using a column chromatography(hexane: E.A=10:1) (0.550 g, 88%).

¹H NMR (CDCl₃): =7.51(d, J=7.6 Hz, 1H, Ph), 7.22 (t, J=7.6 Hz, 1H, Ph),7.07 (t, J=7.6 Hz, 1H, Ph), 6.96 (d, J=7.6 Hz, 1H, Ph), 6.83 (s, 2H,Ph^(Mes)), 6.77 (s, 1H, NH), 2.44 (m, 4H, CH₂*2), 2.46 (s, 6H,Ph^(Mes)), 2.46 (s, 3H, Ph^(Mes)), 1.76 (s, 3H, CH₃)

EXAMPLE 182-(2,5-dimethylcyclopenta-1,4-dienyl)-4-fluorophenyl(2-mesitylenesulfonyl)-amine

0.636 g (1.581 mmol) of CeCl₃ and 15 mL of THF were loaded to a 50 mLflask, and then 2.30 mL (3.677 mmol) of MeLi (1.6 M in diethyl ether)was added thereto at −78° C. 30 minutes after the resultant mixtureturned yellow, 0.500 g (1.290 mmol) of2-(2-(2-mesitylenesulfonyl)amino-4-fluorophenyl)-3-methyl-2-cyclopenten-1-onemelted in 15 mL of THF was added to the flask using a syringe andstirred at −78° C. for 2 hours. The stirred product was stirred for onehour while the temperature was slowly raised. 8 mL of distilled waterwas added to the flask and the THF contained in the reaction product wasremoved using a rotary vacuum evaporator. 8 mL of E.A and 4 mL of 2 NHCl were added to the reaction product from which the THF had beenremoved, and then strongly stirred for 3 minutes. Subsequently, theorganic layer was collected from the stirred reaction product. 4 mL ofE.A was twice added to the aqueous liquid to obtain the organic layer.The collected organic layer was neutralized using 4 mL of NaHCO₃ anddried over MgSO₄ to remove water contained therein. CeCl₃ and MgSO₄ wereremoved using a glass filter and the solvent contained in the driedproduct was removed using a rotary vacuum evaporator. The product wasfiltered using a column chromatography (hexane:E.A=10:1) (0.360 g, 72%).

EXAMPLE 192-(2,5-dimethylcyclopenta-1,4-dienyl)-5-fluorophenyl(2-mesitylenesulfonyl)-amine

0.500 g (1.233 mmol) of2-(2-(2-mesitylenesulfonyl)amino-5-fluorophenyl)-3-methyl-2-cyclopenten-1-oneand 10 mL of THF were added to a 50 mL flask, and then 1.927 ml (3.083mmol) of MeLi (1.6 M in diethyl ether) was added thereto at −78° C. andstirred at the same temperature for 2 hours. The reaction product wasstirred for 2 hours while the temperature was slowly raised. The work-upwas the same as in Example 17 (0.173 g, 35%).

¹H NMR (CDCl₃): =6.88(s, 2H, Ph^(Mes)), 6.84-6.81 (m, 1H, Ph), 6.64-6.61(m, 1H, Ph), 6.09 (s, 1H, NH), 5.89 (s, 1H, CH₂ ^(Cp)), 2.85-2.84 (m,2H, CH₂ ^(Cp)), 2.50 (s, 6H, CH₃*2), 2.31 (s, 3H, CH₃), 1.82 (s, 3H,CH₃), 1.68 (s, 3H, CH₃); ¹³C {¹H} NMR (CDCl₃): =142.94, 142.19, 141.97,141.69, 138.84, 131.53, 125.36, 125.05, 112.78, 112.57, 103.70, 103.45,103.20, 94.58, 44.53, 22.96, 21.02, 14.77, 14.77, 14.49

EXAMPLE 202-(2,5-dimethylcyclopenta-1,4-dienyl)-5-methylphenyl(2-mesitylenesulfonyl)-amine

0.500 g (1.258 mmol) of2-(2-(2-mesitylenesulfonyl)amino-5-methylphenyl)-3-methyl-2-cyclopenten-1-oneand 10 mL of THF were added to a 50 mL flask at −78° C., and 1.965 ml(3.145 mmol) of MeLi (1.6 M in diethyl ether) was added thereto. Thefollowing experiment was the same as in Example 17 (0.182 g, 37%).

¹H NMR (CDCl₃): =7.03(s, 1H, Ph), 6.80 (s, 2H, Ph^(Mes)), 6.65 (s, 1H,Ph), 6.13 (s, 1H, NH), 5.77 (s, 1H, CH₂ ^(Cp)), 2.79-2.60 (m, 2H, CH₂^(cp)), 2.43 (s, 3H, CH₃), 2.36 (s, 6H, CH₃ ^(mes)), 2.31 (s, 3H, CH₃),2.29 (s, 3H, CH₃), 1.70 (s, 3H, CH₃), 1.50 (s, 3H, CH₃); ¹³C {¹H} NMR(CDCl₃): =142.41, 141.45, 140.08, 139.69, 138.78, 137.40, 136.41,134.38, 131.51, 131.36, 130.98, 128.76, 128.45, 124.71, 44.14, 23.43,23.09, 21.05, 20.96, 19.89, 14.71, 14.54

EXAMPLE 21 2-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenylamine

Brown solid was obtained in the same manner as in Example 18 using 9.598g (38.973 mmol) of anhydrous CeCl₃, 24.358 mL (38.973 mmol) of MeLi (1.6M in diethyl ether), and 2.615 g (12.991 mmol) of2-(2-amino)phenyl-3,4-dimethyl-2-cyclopenten-1-one (2.307 g, 89%).

¹H NMR (CDCl₃): δ 1.56(s, 3H, Cp—CH₃), 1.75 (s, 3H, Cp—CH₃), 1.85 (s,3H, Cp—CH₃), 2.82 (s, 2H, Cp—CH₂), 3.55 (br s, 2H, NH₂), 6.62 (dd,J=7.6, 1.6 Hz, 1H, Ph), 6.65 (td, J=7.6, 1.6 Hz, 1H, Ph), 6.82 (dd,J=7.6, 1.6 Hz, 1H, Ph), 6.99 (td, J=7.6, 1.6 Hz, 1H, Ph) ppm. ¹³C{¹H}NMR (CDCl₃): δ 11.67, 13.63, 14.35, 48.80, 114.67, 117.76, 122.79,127.69, 130.13, 133.14, 135.54, 136.73, 139.61, 144.14 ppm.

EXAMPLE 222-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenylamine

Yellow solid was obtained in the same manner as in Example 18 using9.666 g (39.246 mmol) of anhydrous CeCl₃, 24.529 mL (39.246 mmol) ofMeLi (1.6 M in diethyl ether), and 3.000 g (13.082 mmol) of2-(2-amino-3,5-dimethyl)phenyl-3,4-dimethyl-2-cyclopenten-1-one (2.241g, 75%).

¹H NMR (CDCl₃): δ 1.74(s, 3H, Cp—CH₃), 1.93 (s, 3H, Cp—CH₃), 2.04 (s,3H, Cp—CH₃), 2.26 (s, 3H, Ph-CH₃), 2.33 (s, 3H, Ph-CH₃), 3.00 (q, J=2.4Hz, 2H, Cp—CH₂), 3.47 (br s, 2H, NH₂), 6.72 (s, 1H, Ph), 6.91 (s, 1H,Ph) ppm. ¹³C{¹H} NMR (CDCl₃): δ 11.72, 13.61, 14.40, 17.88, 20.55,48.78, 121.78, 122.61, 126.21, 128.20, 129.60, 133.00, 135.66, 136.41,139.85, 140.07 ppm.

EXAMPLE 232-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-fluorophenylamine

Yellow oil was obtained in the same manner as in Example 18 using (4.120g, 16.730 mmol) of anhydrous CeCl₃, 29.206 mL (16.730 mmol) of MeLi (1.6M in diethyl ether), and 1.300 g of (5.577 mmol)2-(2-amino-3,5-difluoro)phenyl-3,4-dimethyl-2-cyclopenten-1-one (0.902g, 70%).

¹H NMR (CDCl₃): δ 1.67(s, 3H, Cp—CH₃), 1.87 (s, 3H, Cp—CH₃), 1.97 (s,3H, Cp—CH₃), 3.96 (br s, 2H, Cp—CH₂), 3.53 (br s, 2H, NH₂), 6.52 (d,J_(H-F)=8.8 Hz, 1H, Ph), 6.76 (t, J_(H-F)=8.8 Hz, 1H, Ph) ppm. ¹³C{¹H}NMR (CDCl₃): δ 11.58, 13.60, 14.35, 48.95, 102.08, 111.67, 125.30,128.98, 133.85, 134.76, 137.83, 137.96, 149.46, 151.96, 152.84, 155.19ppm.

EXAMPLE 24phenylene(2-mesitylenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumbis(dimethylamide)

0.200 g (0.544 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(2-mesitylene-sulfonyl)aminemelted in 4 mL of toluene and 0.122 g (0.544 mmol) of Ti(NMe₂)₄ dilutedin 3 mL of toluene were loaded to a 25 mL flask, and then reacted at 50°C. for 12 hours. Toluene and dimethylamine contained in the reactionproduct was removed in vacuum. The resultant product was solidated usingpentane.

¹H NMR (CDCl₃): =7.19(d, J=7.6 Hz, 1H, Ph), 7.08 (t, J=7.6 Hz, 1H, Ph),6.98 (t, J=7.6 Hz, 1H, Ph), 6.91 (d, J=7.6 Hz, 1H, Ph), 6.58 (s, 2H,Ph^(Mes)), 5.69 (s, 1H, CH₂ ^(Cp)), 3.24 (s, 12H, N—CH₃), 2.64 (s, 6H,CH₃*2), 2.08 (s, 3H, CH₃) 1.74 (s, 6H, CH₃*2)

EXAMPLE 255-fluorophenylene(2-mesitylenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumbis(dimethylamide)

The same experiment as in Example 24 was carried out, using 0.160 g(0.415 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-5-fluorophenyl(2-mesitylenesulfonyl)amineand 0.093 g (0.415 mmol) of Ti(NMe₂)₄.

¹H NMR(C₆D₆): =7.12(d, J=8.0 Hz, 1H, Ph), 6.71 (t, J=8.0 Hz, 1H, Ph),6.57 (s, 2H, Ph^(Mes)), 6.46 (td, J=8.0 Hz, 1H, Ph), 5.70 (s, 2H, CH₂^(Cp)), 3.27 (s, 12H, N—CH₃), 2.67 (s, 6H, CH₃*2), 1.87 (s, 3H, CH₃)1.76 (s, 6H, CH₃*2)

EXAMPLE 264-fluorophenylene(2-mesitylenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumbis(dimethylamide)

The same experiment as in Example 24 was carried out, using 0.158 g(0.392 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-4-fluorophenyl(2-mesitylenesulfonyl)amineand 0.093 g (0.415 mmol) of Ti(NMe₂)₄.

¹H NMR(C₆D₆): =6.69(s, 2H, Ph^(Mes)), 6.66-6.63 (m, 1H, Ph), 6.52-6.47(m, 1H, Ph), 5.76 (s, 2H, CH₂ ^(Cp)), 3.15 (s, 12H, N—CH₃), 2.92 (s, 6H,CH₃*2), 1.96 (s, 6H, CH₃*2), 1.95 (s, 3H, CH₃); ¹³C {¹H} NMR(C₆D₆):=140.50, 137.94, 131.63, 123.78, 112.60, 112.57, 112.39, 112.35, 112.21,104.65, 104.41, 104.15, 51.36, 23.33, 23.30, 20.85, 13.88

EXAMPLE 274-methylphenylene(2-mesitylenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumbis(dimethylamide)

0.172 g (0.435 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-4-methylphenyl(2-mesitylenesulfonyl)amineand 0.093 g (0.415 mmol) of Ti(NMe₂)₄ were reacted at 80° C. Toluene anddimethylamine was removed from the reaction product in vacuum. Theresultant reaction product was solidated using pentane.

EXAMPLE 282-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(p-toluenesulfonyl)amine

The same experiment as in Example 17 was carried out, using 1.000 g(2.93 mmol) of2-(2-(p-toluenesulfonyl)aminophenyl)-3-methyl-2-cyclopenten-1-one and3.660 ml (5.860 mmol) of MeLi (1.6 M in diethyl ether) (0.617 g, 62%).

¹H NMR (CDCl₃): =7.66(d, J=7.6 Hz, 1H, Ph), 7.59 (d, J=7.6 Hz, 2H,Ph^(Ts)), 7.21 (t, J=7.6 Hz, 1H, Ph), 7.15 (d, J=7.6 Hz, 2H, Ph^(Ts)),7.02 (t, J=7.6 Hz, 1H, Ph), 6.90 (d, J=7.6 Hz, 1H, Ph), 6.64 (s, 1H,NH), 5.93 (s, 1H, CH^(Cp)), 3.09-2.85 (m, 2H, CH₂), 2.36 (s, 3H, CH₃),1.67 (s, 3H, CH₃), 1.38 (s, 3H, CH₃); ¹³C {¹H} NMR (CDCl₃): =143.57,142.00, 142.16, 137.32, 134.07, 134.55, 129.90, 129.32, 129.12, 127.95,126.95, 125.38, 123.59, 118.11, 44.50, 21.46, 14.36, 14.05

EXAMPLE 292-(2,5-dimethylcyclopenta-1,4-dienyl)-4-fluorophenyl(p-toluenesulfonyl)amine

The same experiment as in Example 17 was carried out, using 1.000 g(2.93 mmol) of2-(2-(p-toluenesulfonyl)amino-4-fluorophenyl)-3-methyl-2-cyclopenten-1-oneand 3.660 ml (5.860 mmol) of MeLi (1.6 M in diethyl ether) (0.210 g,53%).

¹H NMR (CDCl₃): =7.62(d, J=8.0 Hz, 2H, Ph^(Ts)), 7.20 (d, J=8.0 Hz, 2H,Ph^(Ts)), 6.81-6.76 (m, 1H, Ph), 6.66-6.63 (m, 1H, Ph), 6.45 (s, 1H,NH), 5.87 (d, J=1.6 Hz, 1H, CH^(Cp)), 2.87-2.72 (m, 2H, CH₂), 2.42 (s,3H, CH₃), 1.82 (s, 3H, CH₃), 1.72 (d, J=2.0 Hz, 3H, CH₃); ¹³C {¹H} NMR(CDCl₃): =161.36, 159.38, 158.89, 156.79, 143.05, 142.65, 141.84,137.36, 128.93, 126.64, 124.79, 118.94, 112.73, 103.09, 44.30, 21.45,14.69, 14.44

EXAMPLE 30phenylene(p-toluenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumbis(dimethylamide)

The same experiment as in Example 17 was carried out, using 0.500 g(1.473 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(p-toluenesulfonyl)amine, and0.330 g (1.473 mmol) of Ti(NMe₂)₄. The crystalline structure of theproduct is shown in FIG. 1.

¹H NMR(C₃D₃): =8.12(d, J=8.0 Hz, 1H, Ph), 7.80 (d, J=7.6 Hz, 2H,Ph^(Ts)), 7.14 (t, J=8.0 Hz, 1H, Ph), 6.97 (d, J=8.0 Hz, 1H, Ph), 6.84(t, J=8.0 Hz, 1H, Ph), 6.74 (d, J=8.0 Hz, 2H, Ph^(Ts)), 5.74 (s, 2H,CH^(Cp)), 3.28 (s, 12H, N—CH₃), 1.86 (s, 3H, CH₃), 1.67 (s, 6H, CH₃*2)

EXAMPLE 314-fluorophenylene(p-toluenesulfonylamido)(2,5-dimethylcyclopentadienyltitaniumbis(dimethylamide)

The same experiment as in Example 24 was carried out, using 0.146 g(0.389 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-4-fluorophenyl(p-toluenesulfonyl)amine,and 0.087 g (0.389 mmol) of Ti(NMe₂)₄.

¹H NMR(C₃D₃): =8.22(d, J=8.0 Hz, 2H, Ph^(Ts)), 6.87 (d, J=8.0 Hz, 2H,Ph^(Ts)), 6.65 (d, J=7.6 Hz, 1H, Ph), 6.50 (t, J=7.6 Hz, 1H, Ph), 5.86(s, 2H, CH^(Cp)), 3.28 (s, 12H, N—CH₃), 1.94 (s, 3H, CH₃), 1.89 (s, 6H,CH₃*2)

EXAMPLE 32phenylene(2-mesitylenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumdichloride

0.200 g (0.426 mmol) of C6H₄(2,4,6-Me₃PhSO₂N)(2,5-Me₂Cp)Ti(NMe₂)₂ (insitu chlorinated after NMR measuring) melted in 3 mL of toluene and0.211 g (1.634 mmol) of Me₂SiCl₂ diluted in 1 mL of toluene were loadedto a 20 mL vial, and then reacted for 1 hour. Toluene contained in thereaction product was removed in vacuum. The resultant product wassolidated using pentane (0.190 g, 72%).

¹H NMR(C₃D₃): =6.84(m, 3H, Ph), 6.56 (s, 2H, CH^(Cp)), 6.54 (d, J=7.6Hz, 1H, Ph), 6.52 (s, 2H, Ph^(Mes)), 2.60 (s, 6H, CH₃*2), 1.88 (s, 3H,CH₃), 1.82 (s, 6H, CH₃*2); ¹³C {¹H} NMR(C₃D₃): =155.58, 143.37, 143.22,139.83, 139.32, 132.47, 129.78, 128.53, 126.20, 124.60, 124.04, 114.54,23.61, 20.93, 15.04

EXAMPLE 335-fluorophenylene(2-mesitylenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumdichloride

The same expresiment as in Example 32 was carried out, using 0.182 g of5-FC₆H₃(2,4,6-Me₃PhSO₂N)(2,5-Me₂Cp)Ti(NMe₂)₂ (in situ chlorinated afterNMR measuring) and 0.161 g (1.245 mmol) of Me₂SiCl₂. The product wasmeasured by NM R spectroscopy, but was not identified.

EXAMPLE 344-fluorophenylene(2-mesitylenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumdichloride

The same expresiment as in Example 32 was carried out, using 0.170 g of4-FC₆H₃(2,4,6-Me₃PhSO₂N)(2,5-Me₂Cp)Ti(NMe₂)₂ (in situ chlorinated afterNMR measuring) and 0.152 g (1.176 mmol) of Me₂SiCl₂. The product wasmeasured by NMR spectroscopy, but was not identified.

EXAMPLE 35phenylene(p-toluenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumdichloride

The same expresiment as in Example 32 was carried out, using 0.150 g(0.317 mmol) of C6H₄(4-MePhSO₂N)(2,5-Me₂Cp)Ti(NMe₂)₂ and 0.123 g (0.951mmol) of Me₂SiCl₂ (0.130 g, 88%).

¹H NMR(C₃D₃): =8.14(d, J=7.6 Hz, 2H, Ph^(Ts)), 7.09 (d, J=7.6 Hz, 2H,Ph), 6.94 (t, J=7.6 Hz, 1H, Ph), 6.80 (t, J=7.6 Hz, 1H, Ph), 6.74 (d,J=7.6 Hz, 1H, Ph), 6.61(d, J=7.6 Hz, 2H, Ph^(Ts)), 6.59 (s, 2H,CH^(Cp)), 1.75 (s, 6H, CH₃*2), 1.73.(s, 3H, CH₃)

EXAMPLE 364-fluorophenylene(p-toluenesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumdichloride

The same expresiment as in Example 32 was carried out, using 0.102 g(0.200 mmol) of 4-FC₆H₄(4-MePhSO₂N)(2,5-Me₂Cp)Ti(NMe₂)₂ and 0.077 g(0.601 mmol) of Me₂SiCl₂ (0.080 g, 81%).

¹H NMR(C₃D₃): =8.18(d, J=8.0 Hz, 2H, Ph^(Ts)), 6.73 (d, 1H, CH^(Cp)),6.65 (d, J=8.0 Hz, 2H, Ph^(Ts)), 6.54 (d, 1H, CH^(Cp)), 6.27-6.21 (m,1H, Ph), 6.14-6.12 (m, 1H, Ph), 1.84 (s, 3H, CH₃), 1.79 (s, 3H, CH₃),1.66 (s, 3H, CH₃)

EXAMPLE 372-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(methanesulfonyl)amine

2-(2,5-dimethylcyclopenta-1,4-dienyl)phenylamine (0.500 g, 2.699 mmol)was melted in 5 mL of M.C, and then 0.235 g (2.969 mmol) of pyridine and0.340 g (2.969 mmol) of methanesulfonyl chloride were added thereto. Thereactants were reacted at room temperature for 7 hours. Then, 4 mL of 2N HCl and 10 mL of M.C were added to the reaction product. The organiclayer was collected and dried over MgSO₄ to remove water containedtherein. The solvent contained in the resultant organic layer wasremoved using a rotary vacuum evaporator. The product was filtered using10 mL of diethyl ether, thereby obtaining white solid (0.482 g, 68%).

¹H NMR (CDCl₃): δ 0.92 (d, J=1.6 Hz, 3H, CH₃), 1.89 (s, 3H, CH₃), 2.95(s, 3H, CH₃), 2.99-3.13 (m, 2H, CH₂), 6.03 (d, J=1.6 Hz, 1H, CH), 6.45(s, 1H, NH), 7.09 (dd, J=7.6, 1.6 Hz, 1H, Bz^(3 or 6)), 7.15 (td, J=7.6,1.2 Hz, 1H, Bz^(4 or 5)), 7.33 (td, J=7.6, 1.6 Hz, 1H, Bz^(4 or 5)),7.63 (d, J=7.6 Hz, 1H, Bz^(3 or 6)) ppm.

EXAMPLE 38phenylene(methanesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumbis(dimethylamide)

0.400 g (1.519 mmol) of 2-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(methanesulfonyl)amine and 0.341 g (1.519 mmol) of Ti(NMe₂)₄ were addedto 12 mL of toluene, and then reacted at 50° C. for 12 hours. Thesolvent contained in the reaction product was removed in a reducedpressure. The resultant reaction product was filtered using 10 mL ofpentane in a drybox and then dried in a reduced pressure, therebyobtaining red solid (0.507 g, 84%).

¹H NMR(C₆D₆): δ 1.63 (s, 6H, Cp—CH₃), 2.45 (s, 3H, CH₃), 3.11 (s, 12H,Ti(NMe₂)₃), 5.62 (s, 1H, CH), 6.94 (t, J=7.2 Hz, 1H, BZ^(4 or 5)), 6.94(d, J=7.2 Hz, 1H, BZ^(3 or 6)), 7.16 (t, J=7.2 Hz, 1H, Bz^(4 or 5)),8.04 (d, J=7.2 Hz, 1H, Bz^(3 or 6)) ppm.

EXAMPLE 39phenylene(methanesulfonylamido)(2,5-dimethylcyclopentadienyl)titaniumdichloride

0.400 g (1.007 mmol) of C6H₄(MeSO₂N)(2,5-Me₂Cp)Ti(NMe₂)₂ and 0.390 g(3.020 mmol) Me₂SiCl₂ were added to 10 mL of toluene and then reacted atroom temperature for one hour. By-products contained in the reactionproduct was removed in a reduced pressure. The resultant reactionproduct was filtered using 10 mL of pentane in a drybox and dried in areduced pressure (0.298 g, 78%).

¹H NMR(C₆D₆): δ 1.62 (broad s, 6H, Cp—CH₃), 2.51 (s, 3H, CH₃), 6.41-6.62(broad s, 1H, CH), 6.75 (d, J=7.2 Hz, 1H, Bz^(3 or 6)), 6.86 (t, J=7.2Hz, 1H, Bz^(4 or 5)), 7.01 (t, J=7.2 Hz, 1H, Bz^(4 or 5)), 7.04 (d,J=7.2 Hz, 1H, Bz^(3 or 6))

EXAMPLE 402-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenyl(p-toluenesulfonyl)amine

0.131 g (1.505 mmol) of pyridine and 0.316 g (1.656 mmol) ofp-toluenesulfonyl chloride were added to 0.300 g (1.505 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenylamine melted in 3 mL ofMC, and then reacted at room temperature for 12 hours. 3 mL of 2 N HClwas added to the reaction product and strongly stirred for a fewminutes. The organic layer was collected. The collected organic layerwas neutralized with 3 mL of H₂O without delay and dried over MgSO₄. Theproduct was filtered using a column chromatography withhexane/ethylacetate (v/v=3:1). The solvent contained in the purifiedproduct was dried in vacuum, thereby obtaining white solid (0.340 g,64%).

¹H NMR (CDCl₃): δ 1.32(d, J=1.6 Hz, 3H, CH₃), 1.65 (s, 3H, CH₃), 1.95(s, 3H, CH₃), 2.38 (s, 3H, CH₃), 2.95 (qd, J=19.2, 1.6 Hz, 2H, Cp—CH₂),6.67 (s, 1H, NH), 6.92 (dd, J=7.6, 1.6 Hz, 1H, Ph), 7.05 (td, J=7.6, 1.6Hz, 1H, Ph), 7.15 (d, J=8.0 Hz, 2H, Ts-Ph), 7.24 (td, J=7.6, 1.6 Hz, 1H,Ph), 7.62 (d, J=8.0 Hz, 2H, Ts-Ph), 7.64 (dd, J=7.6, 1.6 Hz, 1H, Ph)ppm. ¹³C{¹H} NMR (CDCl₃): δ 11.09, 14.05, 14.36, 21.46, 44.50, 118.11,123.59, 125.38, 126.95, 127.95, 129.12, 129.32, 129.90, 134.55, 134.07,137.32, 142.16, 142.00, 143.57 ppm.

EXAMPLE 412-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenyl(p-toluenesulfonyl)amine

White solid was obtained in the same manner as in Example 40 using 0.699g (3.075 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenylamine, 0.243g (3.075 mmol) of pyridine, and 0.645 g (3.383 mmol) ofp-toluenesulfonyl chloride (1.009 g, 86%).

¹H NMR (CDCl₃): δ 1.26(d, J=0.8 Hz, 3H, Cp—CH₃), 1.58 (s, 3H, Cp—CH₃),1.71 (s, 3H, Cp—CH₃), 2.20 (s, 3H, Ph-CH₃), 2.31 (s, 3H, Ph-CH₃), 2.37(s, 3H, Ts-CH₃), 2.26-2.58 (m, 2H, Cp—CH₂), 5.95 (s, 1H, NH₁), 6.54 (s,1H, Ph), 6.93 (s, 1H, Ph), 7.03 (d, J=8.0 Hz, 2H, Ts-Ph), 7.35 (d, J=8.0Hz, 2H, Ts-Ph) ppm.

EXAMPLE 422-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-difluorophenyl(p-toluenesulfonyl)amine

White solid was obtained in the same manner as in Example 40 using 0.300g (1.275 mmol)2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-difluorophenylamine, 0.101g (1.275 mmol) of pyridine, and 0.267 g (1.403 mmol)_(p)-toluenesulfonylchloride (0.340 g, 68%).

¹H NMR (CDCl₃): δ 1.53(d, J=1.2 Hz, 3H, Cp—CH₃), 1.78 (s, 3H, Cp—CH₃),1.88 (s, 3H, Cp—CH₃), 2.43 (s, 3H, Ts-CH₃), 3.96 (qd, J=23.2, 1.6 Hz,2H, Cp—CH₂), 6.26 (s, 1H, NH₁), 6.60-6.63 (m, 1H, Ph), 6.77-6.83 (m, 1H,Ph), 7.21 (d, J=8.4 Hz, 2H, Ts-Ph), 7.62 (d, J=8.4 Hz, 2H, Ts-Ph) ppm.¹³C{¹H} NMR (CDCl₃): δ 11.66, 13.48, 14.46, 21.61, 48.78, 103.19,112.70, 118.94, 126.74, 128.94, 133.91, 133.98, 137.40, 137.48, 138.36,143.04, 156.58, 158.97, 161.32 ppm.

EXAMPLE 43phenylene(p-toluenesulfonylamido)(2,3,5-trimethylcyclopentadienyl)titaniumbis(dimethylamide)

0.201 g (0.569 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenyl(p-toluenesulfonyl)amineand 0.128 g (0.569 mmol) of Ti(NMe₂)₄ were added to 6 mL of toluene, andthen reacted at 70° C. for 12 hours. The reaction product was dried toremove all the entire volatile materials in vacuum, and then washedusing 5 mL of pentane, thereby obtaining red solid.

¹H NMR(C₆D₆): δ 1.64(s, 3H, CH₃), 1.70 (s, 3H, CH₃), 1.83 (s, 3H, CH₃),1.89 (s, 3H, CH₃), 3.09 (s, 6H, Ti—NMe₂), 3.50 (s, 6H, Ti—NMe₂), 5.95(s, 1H, Cp—CH), 6.76 (d, J=7.6 Hz, 2H, Ts-Ph), 6.83 (t, J=8.0 Hz, 1H,Ph), 6.98 (d, J=8.0 Hz, 1H, Ph), 7.11 (t, J=8.0 Hz, 1H, Ph), 7.77 (d,J=7.6 Hz, 2H, Ts-Ph), 8.07 (d, J=8.0 Hz, 1H, Ph) ppm

EXAMPLE 444,6-dimethylphenylene(p-toluenesulfonylamido)(2,3,5-trimethylcyclopentadienyl)titaniumbis(dimethylamide)

Red solid was obtained in the same manner as in Example 43 using 0.303 g(0.794 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenyl(p-toluenesulfonyl)amineand 0.179 g (0.794 mmol) of Ti(NMe₂)₄.

¹H NMR(C₆D₆): δ 1.88(s, 3H, CH₃), 1.95 (s, 3H, CH₃), 2.06 (s, 3H, CH₃),2.14 (s, 3H, CH₃), 2.19 (s, 3H, CH₃), 3.23 (s, 6H, Ti—Me₂), 3.43 (s, 6H,Ti—Me₂), 5.93 (s, 1H, Cp—CH), 6.77 (s, 1H, Ph), 6.85 (d, J=5.6 Hz, 2H,Ts-Ph), 6.96 (s, 1H, Ph), 8.23 (d, J=5.6 Hz, 2H, Ts-Ph) ppm. ¹³C{¹H} NMR(C₆D₆): δ 11.69, 13.06, 13.44, 20.60, 21.10, 21.40, 51.89, 52.49,113.91, 120.39, 121.87, 126.87, 127.83, 129.42, 131.49, 131.61, 132.72,133.36, 134.33, 141.97, 142.48, 146.53 ppm

EXAMPLE 454,6-fluorophenylene(p-toluenesulfonylamido)(2,3,5-trimethylcyclopentadienyl)titaniumbis(dimethylamide)

Red solid was obtained in the same manner as in Example 43 using 0.166 g(0.426 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-fluorophenyl(p-toluenesulfonyl)amineand 0.095 g (0.426 mmol) of Ti(NMe₂)₄.

¹H NMR(C₆D₆): δ 1.65(s, 3H, CH₃), 1.88 (s, 3H, CH₃), 1.94 (s, 3H, CH₃),1.99 (s, 3H, CH₃), 3.07 (s, 6H, Ti—Me₂), 3.39 (s, 6H, Ti—Me₂), 5.83 (s,1H, Cp—CH₁), 6.43-6.49 (m, 1H, Ph), 6.60-6.63 (m, 1H, Ph), 6.81 (d,J=8.0 Hz, 2H, Ts-Ph), 8.16 (d, J=8.4 Hz, 2H, Ts-Ph) ppm. ¹³C{¹H} NMR(C₆D₆): δ 11.26, 12.77, 13.00, 21.38, 51.82, 52.74, 104.12, 112.12,114.39, 119.65, 120.24, 121.52, 127.01, 129.40, 131.91, 141.09, 142.35,153.34, 155.80, 157.51, 159.93 ppm

EXAMPLE 46phenylene(p-toluenesulfonylamido)(2,3,5-trimethylcyclopentadienyl)titaniumdichloride

0.228 g (1.707 mmol) of dichlorodimethylsilane and 4 ml of toluene wereadded to C6H₄(4-MePhSO₂N)(2,3,5-Me₃Cp)Ti(NMe₂)₂ that was obtained inExample 43, and then reacted at room temperature for 1 hour. Thereaction product was dried to remove the volatile material in vacuum,and then washed using 3 mL of pentane, thereby obtaining yellow solid(0.228 g, 78%).

¹H NMR(C₆D₆): δ 1.66(br s, 3H, CH₃), 1.79 (s, 6H, CH₃), 2.26 (s, 3H,CH₃), 6.48 (s, 1H, Cp—CH), 6.66 (d, J=8.0 Hz, 2H, Ts-Ph), 6.86-6.88 (m,2H, Ph), 6.99-7.02 (m, 1H, Ph), 7.11-7.13 (m, 2H, Ph), 8.16 (d, J=8.0Hz, 2H, Ts-Ph) ppm. ¹³C{¹H} NMR (C₆D₆): δ 12.80, 15.19, 15.44, 21.41,114.60, 124.57, 124.62, 125.63, 126.84, 128.50, 128.92, 129.27, 129.71,130.01, 135.61, 135.69, 145.03, 155.27 ppm.

EXAMPLE 474,6-dimethylphenylene(p-toluenesulfonylamido)(2,3,5-trimethylcyclopentadienyl)titanium dichloride

0.307 g (2.382 mmol) of dichlorodimethylsilane and 8 mL of toluene wereadded to 4,6-Me₂C6H₄(4-MePhSO₂N)(2,3,5-Me₃Cp)Ti(NMe₂)₂ that was obtainedin Example 44, and then reacted at room temperature for one hour. Thereaction product was dried in vacuum to remove the volatile materialcontained therein, and then washed using 9 mL of pentane, therebyobtaining yellow solid (0.327 g, 76%).

¹H NMR(C₆D₆): δ 1.80(s, CH₃), 1.84 (s, CH₃), 1.90 (s, CH₃), 1.92 (s,CH₃), 1.95 (s, CH₃), 2.11 (s, CH₃), 2.13 (s, CH₃), 2.15 (s, CH₃), 2.28(s, CH₃), 2.29 (s, CH₃), 2.39 (s, CH₃), 6.38 (s, Cp—CH), 6.51 (s,Cp—CH), 6.61-6.64 (m, 2H, Ts-Ph), 6.64 (s, 2H, Ph), 8.08-8.12 (m, 2H,Ts-Ph) ppm.

EXAMPLE 484,6-fluorophenylene(p-toluenesulfonylamido)(2,3,5-trimethylcyclopentadienyl)titaniumdichloride

0.165 g (1.278 mmol) of dichlorodimethylsilane and 4 ml of toluene wereadded to 4,6-F₂C6H₄(4-MePhSO₂N)(2,3,5-Me₃Cp)Ti(NMe₂)₂ that was obtainedin Example 45, and then reacted at room temperature for one hour. Thereaction product was dried in vacuum to remove the volatile materialcontained therein, and then washed using 4 mL of pentane, therebyobtaining yellow solid (0.166 g, 71%).

¹H NMR(C₆D₆): δ 1.61(s, 1.5H, CH₃), 1.72 (s, 1.5H, CH₃), 1.81 (s, 1.5H,CH₃), 1.82 (s, 1.5H, CH₃), 1.83 (s, 1.5H, CH₃), 1.90 (s, 1.5H, CH₃),2.28 (s, 3H, CH₃), 6.26-6.32 (m, 2H, Ph), 6.46 (s, 0.5H, Cp—CH₁), 6.63(s, 0.5H, Cp—CH₁), 6.70 (d, J=8.0 Hz, 2H, Ts-Ph), 8.17-8.20 (m, 2H,Ts-Ph) ppm.

EXAMPLE 492-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(trimethylacetyl)amine

0.130 g (1.29 mmol) of triethylamine and 0.155 g (1.29 mmol) of pivaloylchloride were added to 0.263 g (1.42 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)phenylamine solution melted in 10mL of MC solvent, and then reacted at room temperature for 1 hour. 5 mLof 2N HCl was added to the reaction product and strongly stirred for afew minutes. The organic layer was neutralized using 5 mL of NaHCO₃, andthe product was filtered using a column chromatography with ahexane/ethyl acetate (v/v, 10:1) solvent. The refined product was driedin vacuum to remove the solvent therein, thereby obtaining while solid(0.355 g, 93%).

¹H NMR (CDCl₃): 1.18 (s, 9H, C(CH₃)₃), 1.73 (q, J=1.6 Hz, 3H, Cp—CH₃),1.89 (s, 3H, Cp—CH₃), 3.08-3.07 (m, 2H, Cp—CH₂), 6.05 (d, J=2.0 Hz, 1H,Cp—CH), 7.07 (dd, 1H, J=7.6, 2.0 Hz, 1H, bz-CH), 7.11 (td, J=7.2, 1.2Hz, 1H, bz-CH), 7.33 (td, J=8.4, 2.0 Hz, 1H, bz-CH), 7.54 (s, 1H, NH),8.44 (d, J=8.0 Hz, 1H, bz-CH) ppm; ¹³C{¹H} NMR (CDCl₃): 14.47, 14.64,27.42, 39.84, 44.59, 119.15, 123.14, 125.27, 128.07, 129.28, 136.02,138.36, 142.64, 142.76, 175.93 ppm.

EXAMPLE 502-(2,5-dimethylcyclopenta-1,4-dienyl)-3,5-dimethylphenyl(trimethylacetyl)-amine

An experiment was performed in the same manner as in Example 49 using0.717 g (3.36 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-3,5-dimethylphenylamine, 0.408 g(4.03 mmol) of triethylamine, and 0.486 g (4.03 mmol) of pivaloylchloride. The reaction product was filtered using a columnchromatography with a toluene/MC (v/v, 1:1) solvent. The resultantreaction product was dried in vacuum to remove the solvent therein,thereby obtaining while solid (0.698 g, 70%).

¹H NMR (CDCl₃): 1.17 (s, 9H, C(CH₃)₃), 1.69 (s, 3H, Cp—CH₃), 1.85 (s,3H, Cp—CH₃), 2.24 (s, 3H, bz-CH₃), 2.34 (s, 3H, bz-CH₃), 2.97 (d, J=1.2Hz, 2H, Cp—CH₂), 5.94 (s, 1H, Cp—CH), 6.75 (s, 1H, NH), 6.78 (s, 1H,bz-CH), 7.03 (s, 1H, bz-CH) ppm; ¹³C{¹H} NMR (CDCl₃): 14.54, 14.58,18.74, 21.08, 27.50, 44.19, 123.88, 127.76, 130.41, 131.19, 132.90,134.94, 135.59, 140.14, 143.35, 175.85 ppm.

EXAMPLE 512-(2,5-dimethylcyclopenta-1,4-dienyl)-3,5-fluorophenyl(trimethylacetyl)-amine

Yellow solid was obtained in the same manner as in Example 49 using0.402 g (1.82 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-3,5-fluorophenylamine, 0.202 g(2.18 mmol) of triethylamine, and 0.263 g (2.18 mmol) of pivaloylchloride (0.347 g, 66%).

¹H NMR(C₆D₆): 1.01 (s, 9H, C(CH₃)₃), 1.66 (s, 3H, Cp—CH₃), 1.72 (q,J=2.0 Hz, 3H, Cp—CH₃), 2.65-2.67 (m, 2H, Cp—CH₂), 5.79 (d, J=2.0 Hz, 1H,Cp—CH), 6.36 (s, 1H, NH), 6.52 (s, 1H, bz-CH), 6.54 (s, 1H, bz-CH) ppm;¹³C{¹H} NMR (C₆D₆): 14.60, 14.63, 27.57, 39.28, 44.53, 103.58 (t,J=102.8 Hz, 1C, bz-C—F), 112.41 (dd, J=84.8, 15.2 Hz, bz-C—F), 124.60,141.70, 142.95, 157.34 (d, J=51.6 Hz, 1C, bz-C—F), 159.62 (d, J=51.6 Hz,1C, bz-C—F), 159.84 (d, J=54.8 Hz, 1C, bz-C—F), 162.09 (d, J=48.8 Hz,1C, bz-C—F), 175.52 ppm.

EXAMPLE 522-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenyl(trimethylacetyl)amine

An experiment was performed in the same manner as in Example 49 using0.534 g (2.68 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenylamine, 0.325 g (3.22 mmol)of triethylamine, and 0.388 g (3.22 mmol) of pivaloyl chloride. Thereaction product was purified using a column chromatography with ahexane/ethylacetate (v/v, 5:1) solvent. The purified product was driedin vacuum to remove the solvent therein, thereby obtaining while solid(0.674 g, 89%).

¹H NMR (CDCl₃): 1.17 (s, 9H, C(CH₃)₃), 1.58 (s, 3H, Cp—CH₃), 1.83 (s,3H, Cp—CH₃), 1.98 (s, 3H, Cp—CH₃), 3.01 (s, 2H, Cp—CH₂), 7.05 (dd,J=7.6, 2.0 Hz, 1H, bz-CH), 7.08 (td, 1H, J=7.6, 1.2 Hz, 1H, bz-CH), 7.30(td, J=7.6, 1.6 Hz, 1H, bz-CH), 7.60 (s, 1H, NH), 8.44 (d, J=8.4 Hz, 1H,bz-CH) ppm; ¹³C{¹H} NMR (CDCl₃): 11.46, 13.51, 14.17, 27.29, 39.71,48.87, 118.94, 122.96, 126.21, 127.78, 129.13, 134.27, 134.63, 135.91,137.91, 137.92, 138.67, 175.75 ppm.

EXAMPLE 532-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenyl(trimethylacetyl)-amine

The same experiment as in Example 49 was performed using 0.600 g (2.64mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenylamine, 0.321g (3.17 mmol) of triethylamine, and 0.382 g (3.17 mmol) of pivaloylchloride (0.727 g, 89%).

¹H NMR (CDCl₃): 1.16 (s, 9H, C(CH₃)₃), 1.54 (s, 3H, Cp—CH₃), 1.80 (s,3H, Cp—CH₃), 1.94 (s, 3H, Cp—CH₃), 2.23 (s, 3H, bz-CH₃), 2.33 (s, 3H,bz-CH₃), 2.91 (brd, J=5.6 Hz, 2H, Cp—CH₂), 6.76 (s, 2H, bz-CH), 7.02 (s,1H, NH) ppm; ¹³C{¹H} NMR (CDCl₃): 11.63, 13.50, 18.79, 21.09, 27.46,39.13, 48.64, 127.68, 130.28, 131.18, 132.85, 133.22, 134.79, 135.34,135.47, 135.62, 140.51, 175.77 ppm.

EXAMPLE 542-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-difluorophenyl(trimethylacetyl)-amine

The same experiment as in Example 49 was performed using 0.463 g (1.97mmol) of 2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-fluorophenylamine,0.239 g (2.36 mmol) of triethylamine, and 0.285 g (2.36 mmol) ofpivaloyl chloride (0.400 g, 64%).

¹H NMR (CDCl₃): 1.18 (s, 9H, C(CH₃)₃), 1.58 (s, 3H, Cp—CH₃), 1.82 (s,3H, Cp—CH₃), 1.94 (s, 3H, Cp—CH₃), 2.92 (s, 2H, Cp—CH₂), 6.61 (s, 1H,NH), 6.67 (dq, J=8.4, 2.8 Hz, 1H, bz-CH), 6.86 (td, 1H, J=8.4, 2.4 Hz,1H, bz-CH) ppm; ¹³C{¹H} NMR (CDCl₃): 11.57, 13.48, 14.28, 27.45, 48.86,103.26 (t, J=100.0 Hz, 1C, bz-C—F), 111.97 (dd, J=87.8, 12.4 Hz, 1C,bz-C—F), 133.71, 134.31, 137.47, 138.02, 156.19 (d, J=51.6 Hz, 1C,bz-C—F), 158.69 (d, J=51.6 Hz, 1C, bz-C—F), 158.99 (d, J=54.8 Hz, 1C,bz-C—F), 161.45 (d, J=51.6 Hz, 1C, bz-C—F), 176.00 ppm.

EXAMPLE 55phenylene(t-butylcarboxyamido)(2,5-dimethylcyclopentadienyl)titaniumbis(dimethylamide)

5 mL of toluene was added to 0.203 g (0.700 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(trimethylacetyl)amine and0.156 g (0.700 mmol) of tetrakis(dimethylamino)titanium, and then thereaction solution was stirred at 80° C. for one day. The reactionproduct was dried in vacuum to remove the volatile material therein,thereby obtaining red oil. (100% purity was identified through ¹H and¹³C NMR spectroscope).

¹H NMR(C₆D₆): 1.43 (s, 9H,C(CH₃)₃), 1.94 (s, 6H, Cp—CH₃), 2.97 (s, 12H,N—CH₃), 5.79 (s, 2H, Cp—CH), 7.01 (td, J=8.4, 1.2 Hz, bz-CH), 7.26 (t,d,J=8.4, 1.6 Hz, 1H, bz-CH), 7.30 (d, J=8.0 Hz, 1H, bz-CH), 7.66 (d, J=8.0Hz, 1H, bz-CH) ppm; ¹³C{¹H} NMR (C₆D₆): 14.73 (Cp—CH₃), 29.14 (C(CH₃)₃),39.77 (C(CH₃)₃), 48.35 (N—CH₃), 112.35, 122.81, 125.21, 125.55, 128.54,131.55, 132.86, 144.65, 168.49 ppm.

EXAMPLE 564,6-dimethylphenylene(t-butylcarboxamido)(2,5-dimethylcyclopentadienyl)-titaniumbis(dimethylamide)

7 mL of toluene solvent was added to 0.515 g (1.73 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenyl(trimethylacetyl)amineand 0.388 g (1.73 mmol) of tetrakis(dimethylamino)titanium. The reactionsolution was stirred at 80° C. for 5 days, and then dried in vacuum toremove the volatile material therein, thereby obtaining red oil (almost100% purity was identified through ¹H and ¹³C NMR spectroscope).

¹H NMR(C₆D₆): 1.43 (s, 9H, C(CH₃)₃), 1.97 (s, 6H, Cp—CH₃), 2.25 (s, 3H,bz-CH₃), 2.62 (s, 3H, bz-CH₃), 2.99 (s, 12H, N—CH₃), 5.89 (s, 2H,Cp—CH), 6.98 (s, 1H, bz-CH), 7.08 (s, 1H, bz-CH) ppm; ¹³C{¹H} NMR(C₆D₆): 14.95, 21.15, 21.60, 29.29, 40.30, 48.42, 112.44, 122.68,124.72, 125.78, 130.92, 131.22, 131.38, 136.98, 140.37, 167.22 ppm.

EXAMPLE 574,6-difluorophenylene(t-butylcarboxamido)(2,5-dimethylcyclopentadienyl)-titaniumbis(dimethylamide)

5 mL of toluene solvent was added to 0.277 g (0.87 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-4,6-difluorophenyl(trimethylacetyl)amineand 0.195 g (0.87 mmol) of tetrakis(dimethylamino)titanium. The reactionsolution was stirred at 80° C. for one day, and then dried in vacuum toremove the volatile material therein, thereby obtaining red oil (almost100% purity was identified through ¹H and ¹³C NMR spectroscope).

¹H NMR(C₆D₆): 1.37 (s, 9H, C(CH₃)₃), 1.81 (s, 6H, Cp—CH₃), 2.92 (s, 12H,N—CH₃), 5.79 (s, 2H, Cp—CH), 6.69-6.78 (m, 2H, bz-CH) ppm; ¹³C{¹H} NMR(C₆D₆): 14.51, 29.04, 44.37, 48.29, 103.78 (t, J=108 Hz, 1C, bz-C—F),112.59, 113.69 (dd, J=84.0, 15.2 Hz, 1C, bz-C—F), 123.08, 156.22 (d,J=51.6 Hz, 1C, bz-C—F), 157.52 (d, J=51.6 Hz, 1C, bz-C—F), 158.63 (d,J=51.2 Hz, 1C, bz-C—F), 160.48 (d, J=48.4 Hz, 1C, bz-C—F), 170.32 ppm.

EXAMPLE 58phenylene(t-butylcarboxamido)(2,3,5-trimethylcyclopentadienyl)titaniumbis(dimethylamide)

6 mL of toluene solvent was added to 0.486 g (1.72 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenyl(trimethylacetyl)amine and0.386 g (1.72 mmol) of tetrakis(dimethylamino)titanium. The reactionsolution was stirred at 80° C. for one day, and then the volatilematerial therein was removed, thereby obtaining red oil (100% purity wasidentified through ¹H and ¹³C NMR spectroscope).

¹H NMR(C₆D₆): 1.45 (s, 9H, C(CH₃)₃), 1.88 (s, 3H, Cp—CH₃), 1.94 (s, 3H,Cp—CH₃), 2.03 (s, 3H, Cp—CH₃), 2.81 (s, 6H, N—CH₃), 3.14 (s, 3H, N—CH₃),5.86 (s, 1H, Cp—CH), 7.03 (td, J=7.2, 1.2 Hz, 1H, bz-CH), 7.27 (dd,J=7.6, 0.8 Hz, 1H, bz-CH), 7.30 (td, J=7.6, 1.2 Hz, 1H, bz-CH), 7.70(dd, J=8.0, 0.8 Hz, 1H, bz-CH) ppm; ¹³C{¹H} NMR (C₆D₆): 12.79, 13.06,14.13, 29.12, 39.76, 47.12, 49.85, 115.52, 120.22, 121.21, 121.31,122.78, 125.59, 125.95, 128.48, 131.52, 132.95, 144.69, 168.90 ppm.

EXAMPLE 594,6-dimethylphenylene(t-butylcarboxamido)(2,3,5-trimethylcyclopentadienyl)titaniumbis(dimethylamide)

7 mL of toluene solvent was added to 0.565 g (1.81 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenyl(trimethylacetyl)amineand 0.407 g (1.81 mmol) of tetrakis(dimethylamino)titanium. The reactionsolution was stirred at 110° C. for four days, and then the volatilematerial therein was removed, thereby obtaining red oil (almost 100%purity was identified through ¹H and ¹³C NMR spectroscope).

¹H NMR(C₆D₆): 1.45 (s, 9H, C(CH₃)₃), 1.92 (s, 3H, Cp—CH₃), 1.99 (s, 3H,Cp—CH₃), 2.06 (s, 3H, Cp—CH₃), 2.27 (s, 3H, bz-CH₃), 2.66 (s, 3H,bz-CH₃), 2.83 (s, 6H, N—CH₃), 3.17 (s, 6H, N—CH₃), 5.89 (s, 1H, Cp—CH),6.99 (s, 1H, bz-CH), 7.10 (s, 1H, bz-CH) ppm; ¹³C{¹H} NMR (C₆D₆): 12.85,13.29, 14.37, 21.19, 21.57, 29.26, 40.28, 47.22, 49.98, 115.62, 119.81,120.77, 121.33, 125.13, 126.11, 130.89, 131.13, 131.46, 136.96, 140.39,167.63 ppm.

EXAMPLE 604,6-difluorophenylene(t-butylcarboxamido)(2,3,5-trimethylcyclopentadienyl)titaniumbis(dimethylamide)

5 mL of toluene solvent was added to 0.277 g (0.87 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-difluorophenyl(trimethylacetyl)amineand 0.195 g (0.87 mmol) of tetrakis(dimethylamino)titanium. The reactionsolution was stirred at 80° C. for one day, and then the volatilematerial therein was removed, thereby obtaining red oil (almost 100%purity was identified through ¹H and ¹³C NMR spectroscope).

¹H NMR(C₆D₆): 1.41 (s, 9H, C(CH₃)₃), 1.72 (s, 3H, Cp—CH₃), 1.84 (s, 3H,Cp—CH₃), 2.77 (s, 6H, N—CH₃), 3.09 (s, 3H, N—CH₃), 5.08 (s, 1H, Cp—CH),6.73-6.79 (m, 2H, bz-CH) ppm; ¹³C{¹H} NMR (C₆D₆): 12.67, 12.80, 14.01,29.04, 40.28, 47.11, 49.82, 103.67 (t, J=102.8 Hz, 1C, bz-C—F), 112.75(dd, J=84.8, 15.2 Hz, 1C, bz-C—F), 120.08, 121.24, 121.74, 123.17,156.24 (d, J=54.4 Hz, 1C, bz-C—F), 160.51 (d, J=51.6 Hz, 1C, bz-C—F),170.67 ppm.

EXAMPLE 614,6-dimethylphenylene(t-butylcarboxamido)(2,5-dimethylcyclopentadienyl)titanium(chloride)(dimethylamide)

0.515 g (1.73 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)-4,6-dimethylphenyl-(trimethylacetyl)amineand 0.388 g (1.73 mmol) of Ti(NMe₂)₄ were added to 7 mL of toluene, andthen reacted at 80° C. for 5 days. The reaction product was dried invacuum to remove the entire solvent, thereby obtaining red oil (100%purity was identified through NMR spectroscophy).

¹H NMR(C₆D₆): 1.45 (s, 9H, C(CH₃)₃), 1.99 (s, 6H, CH₃), 2.26 (s, 3H,Ph-CH₃), 2.66 (s, 3H, Ph-CH₃), 2.99 (s, 12H, N—CH₃), 5.88 (s, 2H, Cp-H),7.01 (s, 1H, Ph-H), 7.10 (s, 1H, Ph-H) ppm. ¹³C{¹H} NMR (C₆D₆): 14.95,21.13, 21.62, 29.27, 40.31, 48.41, 112.42, 122.68, 124.75, 125.76,130.97, 131.25, 131.40, 137.03, 140.39, 167.26 ppm.

7 mL of toluene and 10 mL of Me₂SiCl₂ were added to the obtainedbis(dimethylamido)titanium and then reacted at 80° C. for one day. Thereaction product was dried in vacuum to remove the entire volatilematerial, and then washed using 10 mL of pentane, thereby obtaining redsolid (0.340 g, 45%).

¹H NMR(C₆D₆): 1.01 (s, 9H, C(CH₃)₃), 1.95 (s, 3H, Ph-CH₃), 2.02 (s, 6H,Cp—CH₃), 2.18 (s, 3H, N—CH₃), 2.23 (s, 3H, N—CH₃), 2.43 (s, 3H, Ph-CH₃),6.00 (d, J=2.8 Hz, 1H, Cp-H), 6.25 (d, J=2.8 Hz, 1H, Cp-H), 6.83 (s, 1H,Ph-CH), 7.44 (s, 1H, Ph-H) ppm. ¹³C NMR (C₆D₆): 17.42, 18.27, 18.93,21.05, 30.27, 39.91, 40.82, 122.49, 123.52, 124.25, 130.03, 132.01,137.31, 141.55, 145.65, 147.44, 163.65 ppm.

EXAMPLE 62phenylene(t-butylcarboxamido)(2,3,5-trimethylcyclopentadienyl)titanium(chloride)(dimethylamide)

The same experiment as in Example 61 was carried out, using2-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenyl(trimethylacetyl)amine

EXAMPLE 634,6-difluorophenylene(t-butylcarboxamido)(2,3,5-trimethylcyclopentadienyl)titanium(chloride)(dimethylamide)

The same experiment as in Example 61 was carried out, using2-(2,3,5-trimethylcyclopenta-1,4-dienyl)-4,6-difluorophenyl(trimethylacetyl)amine.

EXAMPLE 644,6-difluorophenylene(t-butyliminooxy)(2,5-dimethylcyclopentadienyl)-titaniumdichloride

0.271 g (2.10 mmol) of dichlorodimethylsilane and 5 mL of toluene wereadded to 4,6-F₂C6H₂(t-BuCON)(2,5-Me₂Cp)Ti(NMe₂)₂. The reaction solutionwas stirred at room temperature for 1 hour. The reaction product wasdried in vacuum to remove the volatile material therein, washed using 10mL of pentane solvent, and then dried in vacuum to remove the solvent,thereby obtaining yellow solid. (0.177 g, 60%). The crystallinestructure of the product is illustrated in FIG. 2.

¹H NMR(C₆D₆): 1.33 (s, 9H,C(CH₃)₃), 1.81 (s, 6H, Cp—CH₃), 6.08 (s, 2H,Cp—CH), 6.15 (dq, J=9.2, 3.2 Hz, 1H, bz-CH), 6.54 (tdq, J=8.4, 3.6, 3.2Hz, 1H, bz-CH) ppm; ¹³C{¹H} NMR (C₆D₆): 16.42, 28.64, 42.10, 103.20 (t,J=103.2 Hz, 1C, bz-C—F), 113.85 (dd, J=92.0, 15.2 Hz, 1C, bz-C—F),122.46, 132.43, 157.69 (d, J=51.6 Hz, 1C, bz-C—F), 158.59 (d, J=51.6 Hz,1C, bz-C—F), 160.15 (d, J=54.8 Hz, 1C, bz-C—F), 161.09 (d, J=51.6 Hz,1C, bz-C—F), 168.29 ppm.

EXAMPLE 65(4,6-difluoro)phenylene(t-butyliminooxy)(2,3,5-trimethylcyclopentadienyl)-titaniumdichloride

0.377 g (2.61 mmol) of dichlorodimethylsilane and 5 mL of toluene wereadded to 4,6-F₂C6H₂(t-BuCON)(2,3,5-Me₃Cp)Ti(NMe₂)₂. The reactionsolution was stirred at room temperature for 8 hours. The reactionproduct was dried in vacuum to remove the volatile material, washedusing 10 mL of pentane solvent and then dried in vacuum to remove thesolvent, thereby obtaining yellow solid (0.378 g, 89%).

¹H NMR(C₆D₆): 1.34 (s, 9H, C(CH₃)₃), 1.74 (s, 3H, Cp—CH₃), 1.89 (s, 3H,Cp—CH₃), 2.03 (s, 3H, Cp—CH₃), 5.91 (s, 1H, Cp—CH), 6.24 (dt, J=9.2, 2.4Hz, 1H, bz-CH), 6.57 (tdt, J=8.4, 3.6, 2.0 Hz, 1H, bz-CH) ppm; ¹³C{¹H}NMR (C₆D₆): 14.12, 15.58, 16.69, 28.66, 42.04, 105.39 (t, J=103.2 Hz,1C, bz-C—F), 113.76 (dd, J=92.0, 18.0 Hz, 1C, bz-C—F), 123.83, 130.68,131.35, 135.90, 157.67 (d, J=51.6 Hz, 1C, bz-C—F), 158.67 (d, J=51.6 Hz,1C, bz-C—F), 160.12 (d, J=54.8 Hz, 1C, bz-C—F), 161.17 (d, J=51.6 Hz,1C, bz-C—F), 168.69, 175.45 ppm.

EXAMPLE 66phenylene(t-butylcarboxamido)(2,5-dimethylcyclopentadienyl)dilithiumsalt

1.31 g (4.86 mmol) of2-(2,5-dimethylcyclopenta-1,4-dienyl)phenyl(trimethylacetyl)amine wasmelted in 25 mL of diethyl ether. Then, 2.70 g of nBuLi (2.5 M inhexane) was slowly added thereto at −30° C. and stirred at roomtemperature for 6 hours. The reaction product was filtered using 10 mLof diethyl ether, and the used solvent was removed, thereby obtainingyellow salt in which the number of coordinated diethyl ethers was 0.39.(1.33 g, 89%).

¹H NMR(C₅D₅N): δ 1.35 (s, 9H, C(CH₃)₃), 2.26 (s, 6H, CH₃), 6.28 (s, 2H,Cp-H), 6.90 (td, J=6.8, 1.6 Hz, 1H, H^(4 or 5)), 7.01 (td, J=7.2, 1.6Hz, 1H, H^(4 or 5)), 7.76 (dd, J=7.6, 2.4 Hz, 1H, H^(3 or 6)), 7.89 (d,J=8.0 Hz, 1H, H^(3 or 6)) ppm. ¹³C{¹H} NMR (C₅D₅N): δ 15.57, 29.86,39.81, 103.50, 113.58, 115.13, 119.70, 123.99, 126.33, 131.13, 137.79,153.18, 178.54 ppm.

EXAMPLE 67phenylene(t-butylcarboxamido)(2,3,5-trimethylcyclopentadienyl)dilithiumsalt

An experiment in the same as Example 66 was carried out, using 1.28 g(4.52 mmol) of2-(2,3,5-trimethylcyclopenta-1,4-dienyl)phenyl-(trimethylacetyl)amine.As a result, a yellow salt in which the number of coordinated diethylethers was 0.29. (1.40 g, 92%).

¹H NMR(C₅D₅N): δ 1.35 (s, 9H, C(CH₃)₃), 2.12 (s, 3H, CH₃), 2.28 (s, 3H,CH₃), 2.45 (s, 3H, CH₃), 6.11 (s, 1H, Cp-H), 6.90 (t, J=6.8 Hz, 1H,H^(4 or 5)), 7.02 (t, J=7.2 Hz, 1H, H^(4 or 5)), 7.76 (d, J=7.6 Hz, 1H,H^(3 or 6)), 7.89 (d, J=7.6 Hz, 1H, H^(3 or 6)) ppm. ¹³C{¹H} NMR(C₅D₅N): δ 12.90, 14.73, 15.38, 29.86, 39.77, 104.54, 110.31, 110.73,111.16, 114.19, 119.61, 123.79, 126.32, 131.23, 138.08, 153.28, 178.48ppm.

EXAMPLE 68phenylene(t-butylcarboxamido)(2,5-dimethylcyclopentadienyl)titaniumdimethyl

0.361 g (1.29 mmol) of TiCl₄DME was melted in 16 mL of diethyl ether.Then, 1.61 mL of MeLi (1.6 M in diethyl ether) was added thereto at 0°C. and stirred for 15 minutes. Next, 0.400 g (1.29 mmol) of<C6H₂(t-BuCON)(2,5-Me₂Cp)>Li₂ was added to the reaction product andstirred for 3 hours. The solvent contained in the resultant reactionproduct was removed, and then the product was filtered using 15 mL ofpentane. The used pentane was removed thereby obtaining dark greensolid. (0.320 g, 72%). The crystalline structure of the product isillustrated in FIG. 3.

¹H NMR(C₆D₆): δ 1.12 (s, 6H, T₁-CH₃), 1.36 (s, 9H, C(CH₃)₃), 1.62 (s,6H, Cp—CH₃), 6.46 (s, 2H, Cp-H), 6.85 (td, J=7.2, 1.2 Hz, 1H,H^(4 or 5)), 6.98 (td, J=7.2, 1.2 Hz, 1H, H^(4 or 5)), 7.01-7.04 (m, 2H,H^(3 and 6)) ppm.

EXAMPLE 69phenylene(t-butylcarboxamido)(2,3,5-trimethylcyclopentadienyl)titaniumdimethyl

An experiment was performed in the same manner as in Example 68 using0.331 g (1.18 mmol) of TiCl₄-DME, 1.48 ml of MeLi (1.6M in diethylether), and 0.400 g (1.18 mmol) of <C6H₂(t-BUCON)(2,3,5-Me₃Cp)>Li₂(0.320 g, 75%).

¹H NMR(C₆D₆): δ 0.95 (s, 3H, T₁-CH₃), 1.23 (s, 3H, T₁-CH₃), 1.36 (s, 9H,C(CH₃)₃), 1.51 (s, 3H, Cp—CH₃), 1.66 (s, 3H, Cp—CH₃), 2.16 (s, 3H,Cp—CH₃), 6.25 (s, 1H, Cp-H), 6.87 (t, J=7.2 Hz, 1H, H^(4 or 5)), 6.99(t, J=8.4 Hz, 1H, H^(4 or 5)), 7.03 (d, J=8.0 Hz, 1H, H^(3 or 6)), 7.07(d, J=8.0 Hz, 1H, H^(3 or 6)) ppm.

COMPARATIVE EXAMPLE 1butylidene(2,5-dimethylcyclopentadienyl)(cyclopentadienyl)titaniumdichloride

26.52 g (95.68 mmol.) of normal butyl lithium was added to 10.4 g (47.84mmol) of2-(1-cyclopenta-1,4-dienyl-butyl)-1,3-dimethyl-cyclopenta-1,3-dienemelted in 60 mL of a cold tetrahydrofuran in a nitrogen atmosphere viaschlenkline. Then, the reaction solution was stirred for 12 hours, driedin a reduced pressure to remove a third of the solvent, filtered, andthen washed using hexane, thereby obtaining lithium salt compound withan yield of 95%. The obtained lithium salt (3.38 g) was melted inpyridine to decrease the temperature thereof to −30° C. Separatly, 1.5 g(8.7 mmol) of Ti(NMe₂)₂Cl₂ was melted in toluene and then thetemperature of the resultant solution was decreased to the sametemperature. Then, the prepared two solutions were quickly mixed andreacted for 20 minutes. The reaction product was dried to remove thesolvent and filtered using pentane, thereby obtaining a titan compoundthat is substituted with a dimethyl amino group.

¹H NMR (pyridine-d₅): δ 6.33 (s, 1H, Cp-H), 6.32 (s, 1H, Cp-H), 6.14 (d,J=2.8 Hz, 1H, Me₂Cp-H), 6.08 (d, J=2.8 Hz, 1H, Me₂Cp-H), 5.22 (s, 1H,Cp-H), 5.03 (s, 1H, Cp-H), 3.61 (t, 1H, CHCH₂), 2.99 (d, J=8.4 Hz 12H,NCH₃), 1.95 (s, 3H, CH₃), 1.82 (s, 3H, CH₃), 1.47 (quartet, J=7.2H, 3H,CHCH₃) ppm.

The titan compound that is substituted with a dimethyl amino group wasmelted in 35 mL of pentane, and then 2 eq. of Me₂SiC2 (2.11 mL) wasadded thereto. The reaction solution was reacted for 30 minutes. Then,the red color of the product disappeared and a solid was formed. Onlythe solid was collected, melted with benzene, and then left sat for 12hours. The generated solid was filtered and the used solvent wasremoved, thereby obtaining a titan-containing bridged metallocenecompound (Yield: 50%).

¹H NMR(C₆D₆): δ 6.77 (quartet, J=2.4 Hz, 1H, Cp-H^(3 or 4)), 6.68 (m,1H, Cp-H^(3 or 4)), 6.67 (d, J=4 Hz, 1H, Me₂Cp-H), 6.64 (d, J=4 Hz, 1H,Me₂Cp-H), 5.19 (dd, J=3.2, 2.8 Hz, 1H, Cp-H^(1 or 5)), 5.02 (dd, J=3.2,2.8 Hz, 1H, Cp-H^(1 or 5)), 3.62 (t, 1H, bridge), 1.74 (s, 3H, CH₃),1.59 (s, 3H, CH₃) ppm.

COMPARATIVE EXAMPLE 2 bis(n-butylcyclopentadienyl)zirconium dichloride

The zirconium metal compound was purchased from US Boulder ScientificCo. and directly used for ethylene copolymerization.

COMPARATIVE EXAMPLE 3iso-propylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride

The zirconium metal compound was purchased from US Boulder ScientificCo. and directly used for ethylene homopolymerization.

Ethylene Homopolymerization

EXAMPLE 70 Ethylene Homopolymerization in the Presence of1,2-C6H₄(2,4,6-Me₃PhSO₂N)(2,5-Me₂Cp)TiCl₂

250 mL of toluene solvent was loaded to a 500 mL glass reactor. Then,1.0 mol of the titanium compound that was treated with 25 mol oftriisobutylaluminum compound, and 5.0 mol of trityltetrakis(pentafluorophenyl)borate cocatalyst were sequentially addedthereto. Right after the reactor was shaken in an oil bath at 90° C. for2 minutes at a rate of 300 rpm, ethylene pressure (40 psig) was added tothe reactor to perform polymerization at 90° C. for 5 minutes. Theresidual ethylene gas was removed. Then, excess ethanol was added to thereaction product to induce the polymer precipitation. The obtainedpolymer was washed with ethanol and acetone two to three times,respectively. The washed product was dried in an oven at 80° C. for 12hours or more. The mass of the measured polymer was 3.26 g, and thedegree of activity of the catalyst was 39.1 Kg PE/mmol-Ti hr.

EXAMPLE 71 Ethylene Homopolymerization in the Presence of1,2-C6H₄(4-MePhSO₂N)(2,5-Me₂Cp)TiCl₂

Ethylene homopolymerization was performed in the same manner as inExample 70 using 1.0 mol of the titanium compound. The mass of themeasured polymer was 1.10 g, and the degree of activity of the catalystwas 13.2 Kg PE/mmol-Ti hr.

EXAMPLE 72 Ethylene Homopolymerization in the Presence of1,2-C6H₄(MeSO₂N)(2,5-Me₂Cp)TiCl₂

Ethylene homopolymerization was performed in the same manner as inExample 70 using 1.0 mol of the titanium compound. The mass of themeasured polymer was 0.33 g, and the degree of activity of the catalystwas 4.0 Kg PE/mmol-Ti hr.

COMPARATIVE EXAMPLE 5 Ethylene Homopolymerization in the Presence ofH₃C(CH₂)₃CH(2,5-Me₂Cp)(Cp)TiCl₂

Ethylene homopolymerization was performed for 10 minutes in the samemanner as in Example 70 using 2.5 mol of the titanium compound. The massof the measured polymer was 2.25 g, and the degree of activity of thecatalyst was 5.40 Kg PE/mmol-Ti hr.

Ethylene Copolymerization

EXAMPLE 73 Copolymerization of Low-Pressure Ethylene and 1-octene

250 mL of toluene solvent and a proper amount of 1-octene were added toa 500 mL glass reactor. Then, a 1.0 micromole of a titanium compoundthat was treated with 25 micromole of triisobutylaluminum compound, and5.0 micromole of trityl tetrakis(pentafluorophenyl)borate cocatalystwere sequentially added thereto. The reactor was placed in an oil bathat 90° C., and then 40 psig of ethylene pressure was added to thereactor to perform polymerization for 10 minutes. The residual ethylenegas was removed, and then excess ethanol was added to the reactionproduct to induce the polymer precipitation. The obtained polymer waswashed with ethanol and acetone two to three times, respectively, andthen dried at 80° C. for 12 hours or more.

EXAMPLE 74 Copolymerization of High-Pressure Ethylene and 1-octene

1.0 L of toluene solvent and a proper amount of 1-octene were added to a2 L autoclave reactor. Then, the reactor was preheated at 90° C. and atthe same time, the reactor was filled with 6 bar of ethylene. 5.0micromole of titanium compound that was treated with 125 micromole oftriisobutylaluminum compound, and 25 micromole of trityltetrakis(pentafluorophenyl)borate cocatalyst were sequentially added toa 25 mL catalyst storage tank. At this time, 13 bar of ethylene wasadded to the catalyst storage tank to perform copolymerization for 10minutes. The residual ethylene gas was removed, and then excess ethanolwas added to the polymer solution to induce precipitation. The obtainedpolymer was washed with ethanol and acetone two to three times,respectively, and then dried at 80° C. for 12 hours or more.

EXAMPLE 75 Copolymerization of High-Pressure Ethylene and 1-octene

1.0 L of toluene solvent and 1-octene (fixed at 0.8 M) were added to a 2L autoclave reactor. Then, ethylene copolymerization was carried out inthe same manner as in Example 74 using various titanium compounds (5.0micromole).

EXAMPLE 76 Copolymerization of high-pressure ethylene and 1-octene

1.0 L of hexane solvent and 1-octene (fixed at 0.8 M) were added to a 2L autoclave reactor. Then, ethylene copolymerization was carried out inthe same manner as in Example 74 using various titanium compounds (5.0micromole) at 140° C. at an ethylene pressure of 35 bar.

Properties Measurement (Weight, Activity, Melt Index, Melting Point, andDensity

A melt index (MI) of a polymer was measured using ASTM D-1238 (ConditionE, 190° C., 2.16 Kg weight). A melting point (T_(m)) of the polymer wasa Differential Scanning Calorimeter (DSC) 2920 produced by TA Co. Thatis, the DSC curve of the polymer was obtained by increasing thetemperature to 200° C., maintaining at 200° C. for 5, decreasing to 30°C., and then increasing. The summit of the DSC curve corresponds to amelting point. At this time, the increase and decrease rates of thetemperature were 10° C./min, and the melting point was obtained in asecond temperature increase period.

In order to measure the density of the polymer, a sample that had beentreated with 1,000 ppm of an antioxidant was formed into a sheet havinga thickness of 3 mm and a diameter of 2 cm by a 180° C. press mold, andthen the prepared sheet was cooled to 10° C./min. The cooled sheet wasmeasured using a mettler scale.

EXPERIMENTAL EXAMPLE 1 Copolymerization of Ethylene and 1-octene

Various properties of copolymers prepared according to Example 73 usingtransition metal complexes prepared according to Examples 32, 35, and 39and Comparative Example 1. The results are shown in Table 1.

TABLE 1 Branch Complex 1-octene Polymer Activity (Kg/ Melt Index^(a)Melting Amount used (M) Weight (g) mmol-Ti hr) (g/10 min) Point (° C.)(mol %) Example 32 0.1 2.3 13.8 19.5 89.5 89.5 Example 35 0.1 4.7 28.3Not 96.7 11 measurable Example 35 0.3 2.0 12.0 Not Not 25 measurablemeasurable Example 39 0.1 0.57 3.2 Has not been measured ComparativeExample 1^(b) 0.1 1.09 6.54 Has not been measured ^(a)I₂ value, ^(b)theweight average molecular weight (Mw) of a polymer obtained using acompex of Comparative Example 1 was 108,150

As shown in Table 1, a degree of copolymerization activity of thecatalyst complexes synthesized in Examples 32, 35, and 39 is dependenton a substitutent of nitrogen. For example, the complex that wassynthesized according to Example 35 in which p-toluenesulfonyl wasintroduced to nitrogen, showed high activity compared to other catalystscomplexes having the same concentration of octane. Almost all of thecomplexes having a phenylene bridge according to the present inventionshowed high copolymerization activity, and high reactivity to an olefinmonomer having a large steric hindrance, such as 1-octene, compared towhen the complex having biscyclopentadienyl of Comparative Example 1 wasused.

EXPERIMENTAL EXAMPLE 2 Copolymerization of Ethylene and 1-octene

Properties of copolymers prepared according to Example 74 using thetransition metal complexes synthesized according to Examples 32, 35, and39 were measured. The results are shown in Table 2.

TABLE 2 Melt Melting Complex 1-octene Activity Index^(a) Point Densityused (M) (g/10 min) (g/10 min) (° C.) (g/cc) Example 32 0.3 34.4 6.8108.9 0.915 Example 32 0.5 23.0 16.6 98.7 0.900 Example 32 0.8 16.8 NotNot Not measur- measur- measurable able able Example 35 0.1 55.1 3.02121.7 0.934 Example 35 0.1^(b) 40.8 1.35 122.3 0.935 Example 35 0.3 50.83.70 107.7 0.912 Example 35 0.5 78.4 43 103.0 0.899 Example 35 0.8 87.2103 89.8 0.883 Example 35 1.2 82.3 Not Not 0.865 measur- measur- ableable Example 39 0.1 24.7 60.8^(c) 121.1 0.931 Example 39 0.3 24.2 4.1110.0 0.915 Comparative 0.3 85.2 2.57 121.0 has not been Example 1measured ^(a)I₂ value, ^(b)reaction temperature of 110° C., ^(c)I₂₁value

As shown in Table 2, the complex prepared according to Example 35 showedhigher copolymerization activity than other complexes, and an increaseof the activity continued to some level as the concentration of octeneincreased. Almost all of the complexes showed low activity compared tothe complex of Comparative Example 1, but a copolymer that wassynthesized using the complexes to which a bridge is introducedaccording to the present invention had lower density than when thecomplex having a bisphenylenecyclopentadienyl group of ComparativeExample 1 was used, which indicates high reactivity of the complexaccording to the present invention with respect to an olefin monomerhaving a large steric hindrance, such as 1-octene.

EXPERIMENTAL EXAMPLE 3 Copolymerization of Ethylene and 1-octene

Properties of copolymers prepared according to Example 74 using thetransition metal complexes synthesized according to Examples 35, 46-48,61-64, and 69 and Comparative Examples 2 and 3 were measured. Theresults are shown in Table 3.

TABLE 3 Polymer Activity Melt Melting Complex Mass (Kg/mmol- Index^(a)Point Density used (g) Ti hr) (g/10 min) (° C.) (g/cc) Example 46 80.0496.05 26 92.8 0.877 Example 47 3.39 4.07 2.70 Not 0.891 measurableExample 48 5.06 6.07 0.23 90.7 0.858 Example 61 7.06 8.47 0.14 112.90.879 Example 62 34.96 41.95 0.33 74.8 0.870 Example 63 44.01 52.81 3.85Not 0.852 measurable Example 64 17.03 20.44 0.26 62.0 0.861 Example 6955.70 66.84 0.64 63.4 0.872 Comparative 118.8 142.5 100 120.7 0.939Example 2 Comparative 112.1 134.6 66.4 98.5 0.910 Example 3 ^(a)I₂ value

As shown in Table 3, the complexes in whicht-butylcarbonyl(butylcarbonyl) was introduced to nitrogen preparedaccording to Examples 61 through 64, and 69 showed lowercopolymerization activity than the complexes in which a sulfonyl groupis introduced to a nitrogen prepared according to Example 46. However, apolymer synthesized using the complexes in whicht-butylcarbonyl(butylcarbonyl) was introduced to nitrogen preparedaccording to Examples 61 through 64, and 69 had high molecular weight.The catalyst complexes according to the present invention showed loweractivity than the catalyst complexes of Comparative Example 2 and 3, buta copolymer that was synthesized using the catalyst complexes accordingto the present invention had higher molecular weight and higher polymerdensity of 0.860 g/cc. Thus, the catalyst complexes according to thepresent invention showed excellent copolymerization reactivity.

EXPERIMENTAL EXAMPLE 4 Copolymerization of Ethylene and 1-octene

Properties of copolymers prepared according to Example 76 using thetransition metal complexes synthesized according to Examples 46 and 69.The results are shown in Table 4.

TABLE 4 Polymer Activity Melt Melting Complex Mass (Kg/mmol- Index^(a)Point Density used (g) Ti hr) (g/10 min) (° C.) (g/cc) Example 46 21.3312.80 Has not been measured Example 69 28.89^(b) 11.56 Has not beenmeasured ^(a)I₂ value, ^(b)polymerization for 15 minutes^(a)I₂ value, ^(b) polymerization for 15 minutes

As shown in Table 4, as a result of copolymerization at high temperatureand high pressure, it was found that the catalyst complexes according tothe present invention was stably used for copolymerization at hightemperature of 140° C.

Compared to a conventional transition metal complex having a siliconbridge and an oxido ligand, a transition metal complex according to thepresent invention has a phenylene bridge, so that a monomer easilyapproaches the transition metal complex in terms of structure and apentagon ring structure of the transition metal complex is stablymaintained. By using a catalyst composition including the transitionmetal complex, a polyolefin copolymer having a very low density lessthan 0.910 g/cc can be obtained.

While the present invention has been particularly shown and describedwith reference to exemplary embodiments thereof, it will be understoodby those of ordinary skill in the art that various changes in form anddetails may be made therein without departing from the spirit and scopeof the present invention as defined by the following claims.

1. A transition metal complex of Formula 1:

where R1 and R2 are each independently a hydrogen atom; a C1-C20 alkyl,aryl, or silyl radical; a C1-C20 alkenyl, alkylaryl, or arylalkylradical; or a metalloid radical of Group 14 metal substituted withhydrocarbyl, wherein R1 and R2 can be connected by an alkylidene radicalthat contains a C1-C20 alkyl or aryl radical to form a ring; R4 is eachindependently a hydrogen atom; a halogen radical; or a C1-C20 alkyl oraryl radical, wherein two R4 can be connected to form a fused ringstructure; R3 is a C1-C20 alkyl sulfonyl, aryl sulfonyl, or silylsulfonyl radical; a C1-C20 alkyl carbonyl, aryl carbonyl, or silylcarbonyl radical; C1-C20 alkyl carboxy, or aryl carboxy radical; orC1-C20 alkyl phosphonyl, or aryl phosphonyl radical; M is a transitionmetal of Group 4; and Q1 and Q2 are each independently a halogenradical; a C1-C20 alkyl or aryl amido radical; a C1-C20 alkyl, alkenyl,aryl, alkylaryl, or arylalkyl radical; or a C2-C20 alkylidene radical.2. The transition metal complex of claim 1, being represented by Formula14:

where R1 and R12 are each independently hydrogen atom; or C1-C20 alkyl,aryl, or silyl radical; R14 is each independently hydrogen atom; aC1-C20 alkyl radical; or halogen radical; Q3 and Q4 are eachindependently a halogen radical; C1-C20 alkyl, or aryl amido radical; orC1-C20 alkyl radical; M is a transition metal of Group 4; and R8 is

where Y is a carbon atom or a sulfur atom; R9 is a hydrogen atom; aC1-C20 alkyl, aryl, or silyl radical; or a C1-C20 alkoxy, or aryloxyradical; and when Y is the carbon atom, n is 1, and when Y is the sulfuratom, n is
 2. 3. The transition metal complex of claim 1, beingrepresented by one of the formulae below:

where R10 is a methyl radical, a tosyl radical, a mesityl radical, or at-butyl radical; Q5 and Q6 are each independently a methyl radical, adimethylamido radical, or a chloride radical.
 4. A transition metalcomplex of Formula 2:

where R1 and R2 are each independently a hydrogen atom; a C1-C20 alkyl,aryl, or silyl radical; a C1-C20 alkenyl, alkylaryl, or arylalkylradical; or a metalloid radical of Group 14 metal substituted withhydrocarbyl, wherein R1 and R2 can be connected by an alkylidene radicalthat contains a C1-C20 alkyl or aryl radical to form a ring; R4 is eachindependently a hydrogen atom; a halogen radical; or a C1-C20 alkyl oraryl radical, wherein two R4 are connected to form a fused ringstructure; M is a transition metal of Group 4; Q1 and Q2 are eachindependently a halogen radical; a C1-C20 alkyl or aryl amido radical; aC1-C20 alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical; or aC2-C20 alkylidene radical; G is an oxygen atom or a sulfur atom; and R5is a hydrogen atom; a C1-C20 alkyl or aryl radical; or a C1-C20 aryloxyradical.
 5. The transition metal complex of claim 4, being representedby one of the formulae below:

where R15 is a methyl radical, a t-butyl radical, or a t-butoxy radical;Q5 and Q6 are each independently a methyl radical, a dimethylamidoradical, or a chloride radical; and X is a halogen radical.
 6. Atransition metal complex of Formula 3:

where R1 and R2 are each independently a hydrogen atom; a C1-C20 alkyl,aryl, or silyl radical; a C1-C20 alkenyl, alkylaryl, or arylalkylradical; or a metalloid radical of Group 14 metal substituted withhydrocarbyl, wherein R1 and R2 can be connected by an alkylidene radicalthat contains a C1-C20 alkyl or aryl radical to form a ring; R4 is eachindependently a hydrogen atom; a halogen radical; or a C1-C20 alkyl oraryl radical, wherein two R4 can be connected to form a fused ringstructure; R5 is a hydrogen atom; a C1-C20 alkyl or aryl radical; or aC1-C20 alkoxy or aryloxy radical; M is a transition metal of Group 4; Q1and Q2 are each independently a halogen radical; a C1-C20 alkyl or arylamido radical; a C1-C20 alkyl, alkenyl, aryl, alkylaryl, or arylalkylradical; or a C2-C20 alkylidene radical; and G′ is an oxygen atom or asulfur atom.
 7. The transition metal complex of claim 6, beingrepresented by one of the formulae below:

where R15 is a methyl radical, a t-butyl radical, or a t-butoxy radical;Q5 and Q6 are each independently a methyl radical, a dimethylamidoradical, or a chloride radical; and X is a halogen radical.
 8. Atransition metal complex of Formula 16:

where R1 and R12 are each independently hydrogen atom; or C1-C20 alkyl,aryl, or silyl radical; R14 is each independently a hydrogen atom; aC1-C20 alkyl radical; or a halogen radical; Q3 and Q4 are eachindependently a halogen radical; a C1-C20 alkyl or aryl amido radical;or a C1-C20 alkyl radical R5 is a hydrogen atom; a C1-C20 alkyl or arylradical; or a C1-C20 alkoxy or aryloxy radical; M is a transition metalof Group 4; and G″ is an oxygen atom or a sulfur atom.